Mixed branched eicosyl polysulfide compositions and methods of making same

ABSTRACT

A composition comprising polysulfides, wherein at least about 50 wt. % of the polysulfides are branched C20 to C60 polysulfides represented by general formula R15S1—[S]n—S2R16 wherein R15 and R16 are each independently a branched C10 to C30 alkyl group and wherein n is an integer from 1 to 10. A process of producing a polysulfides crude product comprising one or more branched C20 to C60 polysulfides comprising: (A) reacting a feedstock comprising one or more branched C10 to C30 mercaptans and sulfur in the presence of a catalyst and (B) collecting the polysulfides crude product.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of U.S. patentapplication Ser. No. 15/825,555 filed Nov. 29, 2017, published as U.S.Patent Application Publication No. U.S. 2018/0079718 A1, which is acontinuation-in-part application of U.S. patent application Ser. No.15/669,097 filed Aug. 4, 2017, published as U.S. Patent ApplicationPublication No. U.S. 2017/0334843 A1, which is a continuation-in-partapplication of U.S. patent application Ser. No. 15/632,910 filed Jun.26, 2017, now U.S. Pat. No. 9,938,237, which is a continuation of andclaims priority to U.S. patent application Ser. No. 15/296,837 filedOct. 18, 2016, now U.S. Pat. No. 9,738,601, which is a divisional of andclaims priority to U.S. patent application Ser. No. 14/981,469 filedDec. 28, 2015, now U.S. Pat. No. 9,512,071, and entitled “Mixed DecylMercaptans Compositions and Methods of Making Same,” each of which isincorporated by reference herein in its entirety.

U.S. patent application Ser. No. 15/669,097 is also acontinuation-in-part application of U.S. patent application Ser. No.15/463,867 filed Mar. 20, 2017, now U.S. Pat. No. 9,879,102, which is acontinuation of and claims priority to U.S. patent application Ser. No.15/284,802 filed Oct. 4, 2016, now U.S. Pat. No. 9,631,039, which is adivisional of and claims priority to U.S. patent application Ser. No.14/981,428 filed Dec. 28, 2015, now U.S. Pat. No. 9,512,248, andentitled “Mixed Decyl Mercaptans Compositions and Use Thereof as ChainTransfer Agents,” each of which is incorporated by reference herein inits entirety.

This application is related to U.S. patent application Ser. No.15/284,809 filed Oct. 4, 2016, now U.S. Pat. No. 9,527,090, which is adivisional of and claims priority to U.S. patent application Ser. No.14/981,475 filed Dec. 28, 2015, now U.S. Pat. No. 9,505,011, andentitled “Mixed Decyl Mercaptans Compositions and Use Thereof as MiningChemical Collectors,” each of which is incorporated by reference hereinin its entirety.

TECHNICAL FIELD

The present disclosure relates to compositions containing C₂₀₊polysulfides and/or C₂₀₊ monosulfides and methods of making same. Morespecifically, the present disclosure relates to compositions containingmixed C₂₀₊ polysulfides and/or mixed C₂₀₊ monosulfides, and methods ofmaking same.

BACKGROUND

Polysulfides of the type disclosed herein are individual organicmolecules containing chains of multiple sulfur atoms. Polysulfides areused in diverse applications including lubricants for the miningindustry; sealants for automotive, construction, and marine uses; and tosome extent as flexibilizing hardeners for epoxy adhesives. Polysulfidesare also used as sulfiding agents in synthetic chemistry processes.While processes for making polysulfides from mercaptans are available,preparing individual mercaptans can be costly due numerous purificationsteps required for the feedstock and/or mercaptan product. Somemercaptans can be used as precursors for agriculture chemicals or asnatural gas additives. However, many applications may not require asingle pure mercaptan compound, but could utilize mercaptan mixtures.Thus, there is a need to develop mercaptan compositions suitable forsuch applications, and methods of making same.

SUMMARY

Disclosed herein is a composition comprising polysulfides, wherein atleast about 50 wt. % of the polysulfides are branched C₂₀ to C₆₀polysulfides represented by general formula R¹⁵S¹—[S]_(n)—S²R¹⁶ whereinR¹⁵ and R¹⁶ are each independently a branched C₁₀ to C₃₀ alkyl group andwherein n is an integer from 1 to 10.

Also disclosed herein is a process of producing a polysulfides crudeproduct comprising one or more branched C₂₀ to C₆₀ polysulfidescomprising: (A) reacting a feedstock comprising one or more branched C₁₀to C₃₀ mercaptans and sulfur in the presence of a catalyst and (B)collecting the polysulfides crude product.

Also disclosed herein is a process of producing one or more branched C₂₀to C₆₀ polysulfides comprising: (a) reacting hydrogen sulfide (H₂S) anda feedstock comprising one or more branched C₁₀ to C₃₀ olefins in thepresence of an initiating agent to produce a branched C₁₀₊ mercaptanscrude composition; (b) recovering an intermediate reaction productcomprising one or more branched C₁₀ to C₃₀ mercaptans from the branchedC₁₀₊ mercaptans crude composition; (c) reacting sulfur and theintermediate reaction product comprising one or more branched C₁₀ to C₃₀mercaptans in the presence of a catalyst; and (d) collecting a C₂₀₊polysulfides crude product comprising the one or more branched C₂₀ toC₆₀ polysulfides.

Also disclosed herein is a composition comprising: (A) at least about 25wt. % branched C₂₀ to C₆₀ polysulfides represented by general formulaR¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integer from 1 to 10, wherein R¹⁵and R¹⁶ are each independently a branched C₁₀ to C₃₀ alkyl grouprepresented by Structure K30-A, Structure K30-B, Structure K30-C,Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, orStructure K30-H, wherein * designates an S¹ atom of an R¹⁵S¹ group or anS² atom of an R¹⁶S² group, and wherein R⁹ is a C₁ to C₂₁ alkyl group;and (B) at least about 5 wt. % branched C₂₀ to C₆₀ monosulfidesrepresented by general formula R¹⁷—S—R¹⁸, wherein R¹⁷ and R¹⁸ are eachindependently a branched C₁₀ to C₃₀ alkyl group represented by StructureK30-A, Structure K30-B, Structure K30-C, Structure K30-D, StructureK30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an attachment point with a sulfur atom of the branched C₂₀ toC₆₀ monosulfide, and wherein R⁹ is a C₁ to C₂₁ alkyl group.

Also disclosed herein is a composition comprising: (A) from at leastabout 50 wt. % to at least about 90 wt. % polysulfides, wherein at leastabout 50 wt. % of the polysulfides are branched C₂₀ to C₆₀ polysulfidesrepresented by general formula R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is aninteger from 1 to 10, wherein R¹⁵ and R¹⁶ are each independently abranched C₁₀ to C₃₀ alkyl group represented by Structure K30-A,Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E,Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an S¹ atom of an R¹⁵S¹ group or an S² atom of an R¹⁶S² group,and wherein R⁹ is a C₁ to C₂₁ alkyl group; and (B) from at least about10 wt. % to at least about 30 wt. % monosulfides, wherein at least 50wt. % of the monosulfides are branched C₂₀ to C₆₀ monosulfidesrepresented by general formula R¹⁷—S—R¹⁸, wherein R¹⁷ and R¹⁸ are eachindependently a branched C₁₀ to C₃₀ alkyl group represented by StructureK30-A, Structure K30-B, Structure K30-C, Structure K30-D, StructureK30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an attachment point with a sulfur atom of the branched C₂₀ toC₆₀ monosulfide, and wherein R⁹ is a C₁ to C₂₁ alkyl group.

Also disclosed herein is a composition comprising: (A) at least about 25wt. % branched C₂₀ to C₆₀ polysulfides represented by general formulaR¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integer from 1 to 10, wherein R¹⁵and R¹⁶ are each independently a branched C₁₀ to C₃₀ alkyl grouprepresented by Structure K30-A, Structure K30-B, Structure K30-C,Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, orStructure K30-H, wherein * designates an S¹ atom of an R¹⁵S¹ group or anS² atom of an R¹⁶S² group, and wherein R⁹ is a C₁ to C₂₁ alkyl group;and (B) at least about 5 wt. % branched C₂₀ to C₆₀ monosulfidesrepresented by general formula R¹⁷—S—R¹⁸, wherein R¹⁷ and R¹⁸ are eachindependently a branched C₁₀ to C₃₀ alkyl group represented by StructureK30-A, Structure K30-B, Structure K30-C, Structure K30-D, StructureK30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an attachment point with a sulfur atom of the branched C₂₀ toC₆₀ monosulfide, and wherein R⁹ is a C₁ to C₂₁ alkyl group; and one ormore of the following components (C)-(I): (C) less than about 5 wt. %branched C₁₆ polysulfides; (D) less than about 15 wt. % branched C₆₄polysulfides; (E) less than about 15 wt. % branched C₆₈ polysulfides;(F) less than about 5 wt. % branched C₇₂ polysulfides and/or branchedC₇₆ polysulfides; (G) less than about 1 wt. % branched C₁₆ to C₇₆monosulfides represented by general formula R¹⁷—S—R¹⁸, wherein R¹⁷ andR¹⁸ are each independently a functional group derived from an olefinselected from the group consisting of C₈ monoolefins, C₃₂ monoolefins,C₃₄ monoolefins, C₃₆ monoolefins, and C₃₈ monoolefins, wherein R¹⁷ andR¹⁸ are not both branched C₃₀ monoolefins; (H) less than about 10 wt. %unreacted C₈ to C₃₈ mercaptans; and (I) less than about 10 wt. %non-mercaptan impurities selected from the group consisting of C₈ to C₃₈olefins, C₈ to C₁₄ alkanes, cyclohexane, methylcyclopentane,methylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene,hexamethylbenzene, C₄ to C₁₂ alcohols, 2-ethyl-1-hexanol, and2-ethylhexyl-2-ethylhexanoate.

BRIEF DESCRIPTION OF THE DRAWINGS

For a detailed description of the preferred embodiments of the disclosedcompositions and methods of making same, reference will now be made tothe accompanying drawings in which:

FIG. 1 displays a reaction schematic for addition of hydrogen sulfide(H₂S) to an olefin;

FIG. 2 displays a GC trace of a crude product from an UV initiatedreaction after removal of residual H₂S;

FIG. 3 displays a GC trace of a reaction product from an UV initiatedreaction after removal of lights;

FIG. 4 displays a GC trace of a crude product from an UV initiatedreaction after removal of residual H₂S;

FIG. 5 displays a GC trace of a reaction product from an UV initiatedreaction after removal of lights;

FIG. 6 displays a comparison of GC traces for a product obtained by UVinitiation and a product obtained by acid catalysis. The upperchromatogram is the UV-initiated C₁₀ mercaptan product, and the lowerchromatogram is the acid catalyzed C₁₀ mercaptan product;

FIG. 7 displays a comparison of GC traces for a C₁₀ mercaptan fractionisolated from a product obtained by UV initiation and a C₁₀ mercaptanfraction isolated from a product obtained by acid catalysis, andparticularly, representative GC profiles of the purified C₁₀ mercaptanreaction product. The upper chromatogram is the acid catalyzed C₁₀mercaptan product, and the lower chromatogram is the UV-initiated C₁₀mercaptan product; and

FIG. 8 displays a GC trace of a crude product from a reaction catalyzedby a hydrodesulfurization catalyst after removal of residual H₂S.

FIG. 9 displays a GC trace of a crude product from a reaction catalyzedby a polysulfidization catalyst.

FIG. 10 displays a GC trace of a crude product from a reaction catalyzedby a polysulfidization catalyst after filtration through silica gel.

DETAILED DESCRIPTION

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure, butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2^(nd) Ed (1997) can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Groups of elements of the Periodic Table are indicated using thenumbering scheme indicated in the version of the Periodic Table ofelements published in Chemical and Engineering News, 63(5), 27, 1985. Insome instances, a group of elements can be indicated using a common nameassigned to the group; for example, alkali metals for Group 1 elements,alkaline earth metals (or alkaline metals) for Group 2 elements,transition metals for Groups 3-12 elements, and halogens for Group 17elements.

Regarding claim transitional terms or phrases, the transitional term“comprising”, which is synonymous with “including,” “containing,”“having,” or “characterized by,” is inclusive or open-ended and does notexclude additional, unrecited elements or method steps. The transitionalphrase “consisting of” excludes any element, step, or ingredient notspecified in the claim. The transitional phrase “consisting of” limitsthe scope of a claim to the specified materials or steps and those thatdo not materially affect the basic and novel characteristic(s) of thepresent disclosure as claimed. The term “consisting essentially of”occupies a middle ground between closed terms like “consisting of” andfully open terms like “comprising.” Absent an indication to thecontrary, when describing a compound or composition, “consistingessentially of” is not to be construed as “comprising,” but is intendedto describe the recited component that includes materials which do notsignificantly alter the composition or method to which the term isapplied. For example, a feedstock consisting essentially of a material Acan include impurities typically present in a commercially produced orcommercially available sample of the recited compound or composition.When a claim includes different features and/or feature classes (forexample, a method step, feedstock features, and/or product features,among other possibilities), the transitional terms comprising,consisting essentially of, and consisting of apply only to the featureclass to which is utilized and it is possible to have differenttransitional terms or phrases utilized with different features within aclaim. For example, a method can comprise several recited steps (andother non-recited steps), but utilize a catalyst system preparationconsisting of specific steps, or alternatively, consisting essentiallyof specific steps, but utilize a catalyst system comprising recitedcomponents and other non-recited components.

While compositions and methods are described in terms of “comprising”(or other broad term) various components and/or steps, the compositionsand methods can also be described using narrower terms, such as “consistessentially of” or “consist of” the various components and/or steps.

The terms “a,” “an,” and “the” are intended, unless specificallyindicated otherwise, to include plural alternatives, e.g., at least one.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers, unlessexplicitly indicated otherwise; e.g., a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while ageneral reference to a butyl group includes an n-butyl group, asec-butyl group, an iso-butyl group, and a tert-butyl group.Additionally, the reference to a general structure or name encompassesall enantiomers, diastereomers, and other optical isomers, whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, asthe context permits or requires. For any particular formula or name thatis presented, any general formula or name presented also encompasses allconformational isomers, regioisomers, and stereoisomers that can arisefrom a particular set of substituents.

A chemical “group” is described according to how that group is formallyderived from a reference or “parent” compound, for example, by thenumber of hydrogen atoms formally removed from the parent compound togenerate the group, even if that group is not literally synthesized inthis manner. By way of example, an “alkyl group” can formally be derivedby removing one hydrogen atom from an alkane, while an “alkylene group”can formally be derived by removing two hydrogen atoms from an alkane.Moreover, a more general term can be used to encompass a variety ofgroups that formally are derived by removing any number (“one or more”)of hydrogen atoms from a parent compound, which in this example can bedescribed as an “alkane group,” and which encompasses an “alkyl group,”an “alkylene group,” and materials having three or more hydrogens atoms,as necessary for the situation, removed from the alkane. Throughout, thedisclosure of a substituent, ligand, or other chemical moiety that canconstitute a particular “group” implies that the well-known rules ofchemical structure and bonding are followed when that group is employedas described. When describing a group as being “derived by,” “derivedfrom,” “formed by,” or “formed from,” such terms are used in a formalsense and are not intended to reflect any specific synthetic methods orprocedures, unless specified otherwise or the context requiresotherwise.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g., halogenated hydrocarbon indicates thepresence of one or more halogen atoms replacing an equivalent number ofhydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” is usedherein in accordance with the definition specified by IUPAC: a univalentgroup formed by removing a hydrogen atom from a hydrocarbon.Non-limiting examples of hydrocarbyl groups include ethyl, phenyl,tolyl, propenyl, and the like. Similarly, a “hydrocarbylene group”refers to a group formed by removing two hydrogen atoms from ahydrocarbon, either two hydrogen atoms from one carbon atom or onehydrogen atom from each of two different carbon atoms. Therefore, inaccordance with the terminology used herein, a “hydrocarbon group”refers to a generalized group formed by removing one or more hydrogenatoms (as necessary for the particular group) from a hydrocarbon. A“hydrocarbyl group,” “hydrocarbylene group,” and “hydrocarbon group” canbe acyclic or cyclic groups, and/or can be linear or branched. A“hydrocarbyl group,” “hydrocarbylene group,” and “hydrocarbon group” caninclude rings, ring systems, aromatic rings, and aromatic ring systems,which contain only carbon and hydrogen. “Hydrocarbyl groups,”“hydrocarbylene groups,” and “hydrocarbon groups” include, by way ofexample, aryl, arylene, arene, alkyl, alkylene, alkane, cycloalkyl,cycloalkylene, cycloalkane, aralkyl, aralkylene, and aralkane groups,among other groups, as members.

The term “alkane” whenever used in this specification and claims refersto a saturated hydrocarbon compound. Other identifiers can be utilizedto indicate the presence of particular groups in the alkane (e.g.,halogenated alkane indicates the presence of one or more halogen atomsreplacing an equivalent number of hydrogen atoms in the alkane). Theterm “alkyl group” is used herein in accordance with the definitionspecified by IUPAC: a univalent group formed by removing a hydrogen atomfrom an alkane. Similarly, an “alkylene group” refers to a group formedby removing two hydrogen atoms from an alkane (either two hydrogen atomsfrom one carbon atom or one hydrogen atom from two different carbonatoms). An “alkane group” is a general term that refers to a groupformed by removing one or more hydrogen atoms (as necessary for theparticular group) from an alkane. An “alkyl group,” “alkylene group,”and “alkane group” can be acyclic or cyclic groups, and/or can be linearor branched unless otherwise specified. Primary, secondary, and tertiaryalkyl group are derived by removal of a hydrogen atom from a primary,secondary, and tertiary carbon atom, respectively, of an alkane. Then-alkyl group can be derived by removal of a hydrogen atom from aterminal carbon atom of a linear alkane.

An aliphatic compound is an acyclic or cyclic, saturated or unsaturatedcarbon compound, excluding aromatic compounds. Thus, an aliphaticcompound is an acyclic or cyclic, saturated or unsaturated carboncompound, excluding aromatic compounds; that is, an aliphatic compoundis a non-aromatic organic compound. An “aliphatic group” is ageneralized group formed by removing one or more hydrogen atoms (asnecessary for the particular group) from a carbon atom of an aliphaticcompound. Thus, an aliphatic compound is an acyclic or cyclic, saturatedor unsaturated carbon compound, excluding aromatic compounds. That is,an aliphatic compound is a non-aromatic organic compound. Aliphaticcompounds and therefore aliphatic groups can contain organic functionalgroup(s) and/or atom(s) other than carbon and hydrogen.

The term “substituted” when used to describe a compound or group, forexample, when referring to a substituted analog of a particular compoundor group, is intended to describe any non-hydrogen moiety that formallyreplaces a hydrogen in that group, and is intended to be non-limiting. Agroup or groups can also be referred to herein as “unsubstituted” or byequivalent terms, such as “non-substituted,” which refers to theoriginal group in which a non-hydrogen moiety does not replace ahydrogen within that group. “Substituted” is intended to be nonlimitingand include inorganic substituents or organic substituents.

The term “olefin” whenever used in this specification and claims refersto hydrocarbons that have at least one carbon-carbon double bond that isnot part of an aromatic ring or an aromatic ring system. The term“olefin” includes aliphatic and aromatic, cyclic and acyclic, and/orlinear and branched hydrocarbons having at least one carbon-carbondouble bond that is not part of an aromatic ring or ring system unlessspecifically stated otherwise. Olefins having only one, only two, onlythree, etc., carbon-carbon double bonds can be identified by use of theterm “mono,” “di,” “tri,” etc., within the name of the olefin. Theolefins can be further identified by the position of the carbon-carbondouble bond(s).

The term “alkene” whenever used in this specification and claims refersto a linear or branched aliphatic hydrocarbon olefin that has one ormore carbon-carbon double bonds. Alkenes having only one, only two, onlythree, etc., such multiple bonds can be identified by use of the term“mono,” “di,” “tri,” etc., within the name. For example, alkaminoenes,alkadienes, and alkatrienes refer to linear or branched acyclichydrocarbon olefins having only one carbon-carbon double bond (acyclichaving a general formula of C₁H_(2n)), only two carbon-carbon doublebonds (acyclic having a general formula of C₁H_(2n-2)), and only threecarbon-carbon double bonds (acyclic having a general formula ofC₁H_(2n-4)), respectively. Alkenes can be further identified by theposition of the carbon-carbon double bond(s). Other identifiers can beutilized to indicate the presence or absence of particular groups withinan alkene. For example, a haloalkene refers to an alkene having one ormore hydrogen atoms replaced with a halogen atom.

The term “alpha olefin” as used in this specification and claims refersto an olefin that has a carbon-carbon double bond between the first andsecond carbon atoms of the longest contiguous chain of carbon atoms. Theterm “alpha olefin” includes linear and branched alpha olefins unlessexpressly stated otherwise. In the case of branched alpha olefins, abranch can be at the 2 position (a vinylidene) and/or the 3 position orhigher with respect to the olefin double bond. The term “vinylidene”whenever used in this specification and claims refers to an alpha olefinhaving a branch at the 2 position with respect to the olefin doublebond. By itself, the term “alpha olefin” does not indicate the presenceor absence of other carbon-carbon double bonds unless explicitlyindicated.

The term “normal alpha olefin” whenever used in this specification andclaims refers to a linear aliphatic mono-olefin having a carbon-carbondouble bond between the first and second carbon atoms. It is noted that“normal alpha olefin” is not synonymous with “linear alpha olefin” asthe term “linear alpha olefin” can include linear olefinic compoundshaving a double bond between the first and second carbon atoms.

The terms “lights,” “light fraction,” or “light compounds” whenever usedin this specification and claims refers to compounds present in thereaction product with equal to or less than about 9 carbon atoms (C⁹⁻)per molecule. Nonlimiting examples of C⁹⁻ compounds that can be in thereaction product include C⁹⁻ monoolefins (e.g., unreacted C⁹⁻monoolefins), C⁹⁻ mercaptans, C⁹⁻ alkanes, C⁹⁻ alcohols, cyclohexane,methylcyclopentane, methylcyclohexane, benzene, toluene, ethylbenzene,xylene, mesitylene, 2-ethyl-1-hexanol, and the like, or combinationsthereof. Unless otherwise specifically indicated herein, the terms“lights,” “light fraction,” or “light compounds” whenever used in thisspecification and claims excludes hydrogen sulfide, as H₂S is typicallysubstantially consumed during the preceding reaction and/or removed fromthe reaction product (as discussed in more detail herein) prior tofurther processing of the reaction product (e.g., distillation thereof).For example, H₂S can be removed from the reaction product viadistillation, stripping, flashing, or other suitable means known tothose of skill in the art without removing any substantial amounts ofthe “lights,” “light fraction,” or “light compounds” from the reactionproduct. Not wanting to be limited by theory, this definition of“lights,” “light fraction,” or “light compounds” includes any compoundswith about nine or less carbon atoms present in the reaction productthat can be detected, even in trace amounts. As is known to one of skillin the art, the light fraction can also contain trace amounts of lowercarbon number sulfides.

The terms “intermediates” or “intermediate fraction” whenever used inthis specification and claims typically refers to compounds with aboutten to seventeen carbon atoms (C₁₀₋₁₇) per molecule. Nonlimitingexamples of C₁₀₋₁₇ compounds include C₁₀ mercaptans (including bothbranched and non-branched C₁₀ mercaptans), C₁₂₋₁₇ mercaptan isomers,C₁₂-C₁₇ sulfides, and the like, or combinations thereof. Not wanting tobe limited by theory, this definition of “intermediates” or“intermediate fraction” includes any compounds with about ten toseventeen carbon atoms present in the reaction product that can bedetected, even in trace amounts. As is known to one skilled in the art,the intermediate fraction can also contain trace amounts of lower carbonnumber compounds, including sulfides. In some embodiments (e.g., in theExamples described herein), a product can be recovered from theintermediate fraction (e.g., a C₁₀ mercaptan fraction), and theremaining C₁₁ to C₁₇ compounds (e.g., C₁₂₋₁₆ mercaptans) can be referredto as the intermediate fraction.

The terms “heavies” or “heavy fraction” whenever used in thisspecification and claims refers to compounds with about eighteen or morecarbon atoms (C₁₈₊) per molecule. Nonlimiting examples of C₁₈₊ productsinclude C₁₈ sulfides, C₂₀ sulfides, C₂₄ sulfides, C₂₈ sulfides, C₃₂sulfides, C₁₈ mercaptans, and the like, or combinations thereof. As isknown to those of skill in the art, the heavy fraction can also containtrace amounts of lower carbon number compounds, including mercaptans andsulfides.

These light, intermediate, and heavy fractions can be referred to as“rough-cuts,” in that they contain a plurality of compounds spreadacross a range of carbon atoms, i.e., a plurality of compounds having adifferent number of carbon atoms (e.g., a rough cut comprising C₁₀, C₁₁,C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, etc. compounds). These rough cuts are incontrast to one or more “fine-cuts” that contain a fewer number ofcompounds than the rough-cuts, for example, a C₁₀ fine cut (e.g., a C₁₀mercaptan fraction) derived from or otherwise recovered separately fromthe rough cut. Accordingly, a rough cut can be comprised of a number offine cuts, for example where a plurality of cuts are taken viadistillation over a period of time and across a ramped temperaturerange, and referred to collectively as a rough cut or individually asfine cuts. Those of ordinary skill in the art can produce a fine-cutfraction from a rough-cut fraction, for example via further distillation(e.g., a C₁₀ splitter, a C₂₀ splitter, etc.) or other purificationtechnique.

The terms “room temperature” or “ambient temperature” are used herein todescribe any temperature from 15° C. to 35° C. wherein no external heator cooling source is directly applied to the reaction vessel.Accordingly, the terms “room temperature” and “ambient temperature”encompass the individual temperatures and any and all ranges, subranges,and combinations of subranges of temperatures from 15° C. to 35° C.wherein no external heating or cooling source is directly applied to thereaction vessel. The term “atmospheric pressure” is used herein todescribe an earth air pressure wherein no external pressure modifyingmeans is utilized. Generally, unless practiced at extreme earthaltitudes, “atmospheric pressure” is about 1 atmosphere (alternatively,about 14.7 psi or about 101 kPa).

Features within this disclosure that are provided as a minimum value canbe alternatively stated as “at least” or “greater than or equal to” anyrecited minimum value for the feature disclosed herein. Features withinthis disclosure that are provided as a maximum value can bealternatively stated as “less than or equal to” or “below” any recitedmaximum value for the feature disclosed herein.

Within this disclosure, the normal rules of organic nomenclature willprevail. For instance, when referencing substituted compounds or groups,references to substitution patterns are taken to indicate that theindicated group(s) is (are) located at the indicated position and thatall other non-indicated positions are hydrogen. For example, referenceto a 4-substituted phenyl group indicates that there is a non-hydrogensubstituent located at the 4 position and hydrogens located at the 2, 3,5, and 6 positions. By way of another example, reference to a3-substituted naphth-2-yl indicates that there is a non-hydrogensubstituent located at the 3 position and hydrogens located at the 1, 4,5, 6, 7, and 8 positions. References to compounds or groups havingsubstitutions at positions in addition to the indicated position will bereferenced using comprising or some other alternative language. Forexample, a reference to a phenyl group comprising a substituent at the 4position refers to a phenyl group having a non-hydrogen substituentgroup at the 4 position and hydrogen or any non-hydrogen group at the 2,3, 5, and 6 positions.

Use of the term “optionally” with respect to any element of a claim isintended to mean that the subject element is required, or alternatively,is not required. Both alternatives are intended to be within the scopeof the claim.

Unless otherwise specified, any carbon-containing group for which thenumber of carbon atoms is not specified can have, according to properchemical practice, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 carbonatoms, or any range or combination of ranges between these values. Forexample, unless otherwise specified, any carbon-containing group canhave from 1 to 30 carbon atoms, from 1 to 25 carbon atoms, from 1 to 20carbon atoms, from 1 to 15 carbon atoms, from 1 to 10 carbon atoms, orfrom 1 to 5 carbon atoms. Moreover, other identifiers or qualifyingterms can be utilized to indicate the presence or absence of aparticular substituent, a particular regiochemistry and/orstereochemistry, or the presence or absence of a branched underlyingstructure or backbone.

Processes and/or methods described herein utilize steps, features, andcompounds which are independently described herein. The process andmethods described herein may or may not utilize step identifiers (e.g.,1), 2), etc., a), b), etc., or i), ii), etc.), features (e.g., 1), 2),etc., a), b), etc., or i), ii), etc.), and/or compound identifiers(e.g., first, second, etc.). However, it should be noted that processesand/or methods described herein can have multiple steps, features (e.g.,reagent ratios, formation conditions, among other considerations),and/or multiple compounds having the same general descriptor.Consequently, it should be noted that the processes and/or methodsdescribed herein can be modified to use an appropriate step or featureidentifier (e.g., 1), 2), etc., a), b), etc., or i), ii), etc.) and/orcompound identifier (e.g., first, second, etc.) regardless of step,feature, and/or compound identifier utilized in a particular aspectand/or embodiment described herein and that step or feature identifierscan be added and/or modified to indicate individual differentsteps/features/compounds utilized within the process and/or methodswithout detracting from the general disclosure.

Embodiments disclosed herein can provide the materials listed assuitable for satisfying a particular feature of the embodiment delimitedby the term “or.” For example, a particular feature of the disclosedsubject matter can be disclosed as follows: Feature X can be A, B, or C.It is also contemplated that for each feature the statement can also bephrased as a listing of alternatives such that the statement “Feature Xis A, alternatively B, or alternatively C” is also an embodiment of thepresent disclosure whether or not the statement is explicitly recited.

The weight percent compositional aspects of the various compositionsdescribed herein (e.g., the weight percent of one or more compoundspresent in a composition) can be determined by gas chromatography (GC),gas chromatography-mass spectroscopy (GC-MS), Raman spectroscopy,nuclear magnetic resonance (NMR) spectroscopy, or any other suitableanalytical method known to those of skill in the art. For example,unless otherwise indicated, the weight percent compositional aspects ofthe various compositions described herein (e.g., the weight percent ofthe various sulfur-containing compounds such as C₁₀ mercaptans and C₂₀sulfides present in the compositions such as the crude, light fraction,intermediate fraction, heavy faction, etc.) can be determined using agas chromatograph with a flame ionization detector (GC-FID) detectorbased on the total GC peak areas (as described herein) and reported asgas chromatography (GC) area percent (GC area %), which is a commonanalytical technique for compositions comprising sulfur-containingcompounds. While not wishing to be bound by this theory, it is believedthat the amount in area % is very similar to the amount in weightpercent (wt. %), and these respective amounts need not be exactlyequivalent or interchangeable in order to be understood by a person ofordinary skill.

In an embodiment, a process of the present disclosure comprisesreacting, in a reactor, hydrogen sulfide (H₂S) and a feedstockcomprising one or more branched C₁₀ monoolefins in the presence of aninitiating agent to produce a crude composition (also referred to as acrude product); wherein the branched C₁₀ monoolefins comprise5-methyl-1-nonene, 3-propyl-1-heptene, 4-ethyl-1-octene,2-butyl-1-hexene, or combinations thereof; and wherein the crudecomposition comprises branched C₁₀ mercaptans and branched C₂₀ sulfides.

The crude composition can be further processed, for example viadistillation, to yield one or more products (also referred to asdistilled, purified, refined, finished, or final products) selected fromthe group consisting of mercaptan compositions (e.g., a compositioncomprising one or more branched C₁₀ mercaptans), sulfide compositions(e.g., a composition comprising one or more branched C₂₀ sulfides); andcompositions having both mercaptans (e.g., branched C₁₀ mercaptans) andsulfides (e.g., branched C₂₀ sulfides), referred to as mercaptan/sulfidecompositions.

In an embodiment, a mercaptan composition comprises branched C₁₀mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane, 3-propyl-1-mercapto-heptane,4-ethyl-1-mercapto-octane, 2-butyl-1-mercapto-hexane,5-methyl-2-mercapto-nonane, 3-propyl-2-mercapto-heptane,4-ethyl-2-mercapto-octane, 5-methyl-5-mercapto-nonane, and combinationsthereof.

In an embodiment, a sulfide composition comprises branched C₂₀ sulfidesrepresented by the structure R¹—S—R², wherein R¹ and R² are eachindependently a functional group derived from an olefin, wherein theolefin comprises 5-methyl-1-nonene, 3-propyl-1-heptene,4-ethyl-1-octene, 2-butyl-1-hexene, or combinations thereof.

In an embodiment, a mercaptan/sulfide composition comprises (A) branchedC₁₀ mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane, 3-propyl-1-mercapto-heptane,4-ethyl-1-mercapto-octane, 2-butyl-1-mercapto-hexane,5-methyl-2-mercapto-nonane, 3-propyl-2-mercapto-heptane,4-ethyl-2-mercapto-octane, 5-methyl-5-mercapto-nonane, and combinationsthereof; and (B) branched C₂₀ sulfides represented by the structureR¹—S—R², wherein R¹ and R² are each independently a functional groupderived from an olefin, wherein the olefin comprises 5-methyl-1-nonene,3-propyl-1-heptene, 4-ethyl-1-octene, 2-butyl-1-hexene, or combinationsthereof.

The mercaptan compositions, sulfide compositions, and mercaptan/sulfidecompositions can be salable or otherwise used for a variety of end usessuch as mining ore collector compositions and chain transfer agents.

In an embodiment, the compositions disclosed herein can be prepared by aprocess comprising reacting, in a reactor, hydrogen sulfide (H₂S) and afeedstock comprising one or more branched C₁₀ monoolefins in thepresence of an initiating agent to produce a crude (reaction product)composition, wherein the branched C₁₀ monoolefins comprise5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

Any feedstock comprising one or more branched C₁₀ monoolefins of thetype described herein can be used, for example a feedstock obtained froma commercial petroleum refining or petrochemical process. Suchfeedstocks can comprise other olefins in addition to the one or morebranched C₁₀ monoolefins of the type described herein, for examplelinear C₁₀ monoolefins as well as olefins having more or less than 10carbon atoms. In an embodiment, the feedstock comprises one or morebranched C₁₀ monoolefins and is obtained from a 1-hexene productionprocess effluent stream. In various embodiments, a feedstock obtainedfrom a 1-hexene production process effluent stream can comprise C₁₀monoolefins (e.g., branched and/or linear C₁₀ monoolefins) as well asolefins having more or less than 10 carbon atoms.

In an embodiment, the feedstock can comprise (a) at least about 76 mol%, alternatively at least about 78 mol %, alternatively at least about80 mol %, or alternatively at least about 82 mol % C₁₀ monoolefins, and(b) at least about 1 mol %, alternatively at least about 2 mol %,alternatively at least about 3 mol %, or alternatively at least about 4mol % C₁₄ monoolefins. In an embodiment, the feedstock can comprise (a)from about 76 mol % to about 92 mol %, alternatively from about 78 mol %to about 90 mol %, alternatively from about 80 mol % to about 88 mol %,or alternatively from about 82 mol % to about 86 mol % C₁₀ monoolefins;and (b) from about 1 mol % to about 12 mol %, alternatively from about 2mol % to about 10 mol %, alternatively from about 3 mol % to about 8 mol%, or alternatively from about 4 mol % to about 7 mol % C₁₄ monoolefins.For purposes of the disclosure herein, a feedstock comprising (a) atleast about 76 mol % C₁₀ monoolefins, and (b) at least about 1 mol % C₁₄monoolefins can also be referred to as a “first feedstock.” In anembodiment, the first feedstock is obtained from a 1-hexene productionprocess effluent stream, for example an effluent stream obtained from a1-hexene production process of the type disclosed in co-pendingInternational Patent Application PCT/US2015/40433, which is incorporatedby reference herein in its entirety.

In another embodiment, the feedstock can comprise at least about 95 mol%, alternatively at least about 96 mol %, alternatively at least about97 mol %, alternatively at least about 98 mol %, or alternatively atleast about 99 mol % C₁₀ monoolefins. For purposes of the disclosureherein, a feedstock comprising at least about 95 mol % C₁₀ monoolefinscan also be referred to as a “second feedstock.” In an embodiment, thesecond feedstock can be produced by purifying the first feedstock, suchas for example by distillation of an effluent stream obtained from a1-hexene production process of the type disclosed in co-pendingInternational Patent Application PCT/US2015/40433, which is incorporatedby reference herein in its entirety.

In an embodiment, the C₁₀ monoolefins of any feedstock described herein(e.g., a first feedstock or a second feedstock) can comprise, canconsist essentially of, or can be, 2-butyl-1-hexene, 3-propyl-1-heptene,4-ethyl-1-octene, and 5-methyl-1-nonene. In an embodiment, the C₁₀monoolefins of any feedstock described herein can comprise i) at leastabout 3 mol %, alternatively at least about 4 mol %, alternatively atleast about 5 mol %, alternatively at least about 6 mol %, alternativelyat least about 7 mol %, or alternatively at least about 8 mol %2-butyl-1-hexene (represented by Structure L), ii) at least about 8 mol%, alternatively at least about 9 mol %, alternatively at least about 10mol %, alternatively at least about 11 mol %, alternatively at leastabout 12 mol %, or alternatively at least about 13 mol %3-propyl-1-heptene (represented by Structure J), iii) at least about 6mol %, alternatively at least about 7 mol %, alternatively at leastabout 8 mol %, alternatively at least about 9 mol %, alternatively atleast about 10 mol %, or alternatively at least about 11 mol %4-ethyl-1-octene (represented by Structure K), and iv) at least about 20mol %, alternatively at least about 22 mol %, alternatively at leastabout 24 mol %, alternatively at least about 26 mol %, alternatively atleast about 28 mol %, or alternatively at least about 30 mol %5-methyl-1-nonene (represented by Structure I).

In an embodiment, the C₁₀ monoolefins of any feedstock described herein(e.g., a first feedstock or a second feedstock) can have a molar ratioof 2-butyl-1-hexene to 5-methyl-1-nonene of at least about 2:1,alternatively at least about 2.4:1, alternatively at least about 2.6:1,or alternatively at least about 2.8:1. In an embodiment, the C₁₀monoolefins of any feedstock described herein can have a molar ratio of3-propyl-1-heptene to 5-methyl-1-nonene of at least about 1.2:1,alternatively at least about 1.4:1, alternatively at least about 1.6:1,or alternatively at least about 1.8:1. In an embodiment, the C₁₀monoolefins of any feedstock described herein can have a molar ratio of4-ethyl-1-octene to 5-methyl-1-nonene of at least about 1.6:1,alternatively at least about 1.7:1, alternatively at least about 1.9:1,or alternatively at least about 2.1:1. In an embodiment, the C₁₀monoolefins of any feedstock described herein can have a molar ratio of2-butyl-1-hexene to 5-methyl-1-nonene of at least about 2:1,alternatively at least about 2.4:1, alternatively at least about 2.6:1,or alternatively at least about 2.8:1; a molar ratio of3-propyl-1-heptene to 5-methyl-1-nonene of at least about 1.2:1,alternatively at least about 1.4:1, alternatively at least about 1.6:1,or alternatively at least about 1.8:1; and a molar ratio of4-ethyl-1-octene to 5-methyl-1-nonene of at least about 1.6:1,alternatively at least about 1.7:1, alternatively at least about 1.9:1,or alternatively at least about 2.1:1.

In an embodiment, the C₁₀ monoolefins of any feedstock described herein(e.g., a first feedstock or a second feedstock) can comprise linear C₁₀monoolefins. In such embodiment, the linear C₁₀ monoolefins cancomprise, can consist essentially of, or can be, 1-decene, 4-decene,5-decene, or combinations thereof; alternatively, 1-decene;alternatively, 4-decene and/or 5-decene; alternatively, 4-decene; oralternatively, 5-decene. In an embodiment, the C₁₀ monoolefins of anyfeedstock described herein can comprise less than or equal to about 26mol %, alternatively less than or equal to about 24 mol %, alternativelyless than or equal to about 22 mol %, alternatively less than or equalto about 20 mol %, or alternatively less than or equal to about 18 mol %linear C₁₀ monoolefins. In an embodiment, the C₁₀ monoolefins of anyfeedstock described herein can comprise from about 1 mol % to about 16mol %, alternatively from about 2 mol % to about 15 mol %, alternativelyfrom about 3 mol % to about 14 mol %, alternatively from about 4 mol %to about 13 mol %, or alternatively from about 6 mol % to about 12 mol %4-decene and/or 5-decene. In some embodiments, the C₁₀ monoolefins ofany feedstock described herein can comprise less than or equal to about10 mol %, alternatively less than or equal to about 9 mol %,alternatively less than or equal to about 8 mol %, alternatively lessthan or equal to about 7 mol %, or alternatively less than or equal toabout 6 mol % 1-decene. In other embodiments, the C₁₀ monoolefins of anyfeedstock described herein can comprise from about 0.5 mol % to about 9mol %, alternatively from about 1 mol % to about 8 mol %, alternativelyfrom about 1.5 mol % to about 7 mol %, or alternatively from about 2 mol% to about 6 mol %1-decene.

In an embodiment, the first feedstock disclosed herein can furthercomprise C⁹⁻ monoolefins, C₁₁₊ monoolefins, or combinations thereof;alternatively, C⁹⁻ monoolefins; or alternatively, C₁₁₊ monoolefins. Inan embodiment, the C⁹⁻ monoolefins can comprise, can consist essentiallyof, or can be, a C₇ monoolefin, a C₈ monoolefin, a C₉ monoolefin, orcombinations thereof; alternatively, a C₇ monoolefin; alternatively, aC₈ monoolefin; or alternatively, a C₉ monoolefin. In some embodiments,the C⁹⁻ monoolefins can comprise, can consist essentially of, or can be,a C₈ monoolefin. In an embodiment, the monoolefins can comprise, canconsist essentially of, or can be, a C₁₁ monoolefin, a C₁₂ monoolefin, aC₁₃ monoolefin, a C₁₄ monoolefin, a C₁₅ monoolefin, a C₁₆ monoolefin, aC₁₇ monoolefin, a C₁₈ monoolefin, or combinations thereof;alternatively, a C₁₁ monoolefin; alternatively, a C₁₂ monoolefin;alternatively, a C₁₃ monoolefin; alternatively, a C₁₄ monoolefin;alternatively, a C₁₅ monoolefin; alternatively, a C₁₆ monoolefin;alternatively, a C₁₇ monoolefin; or alternatively, a C₁₈ monoolefin. Insome embodiments, the C₁₁₊ monoolefins can comprise, can consistessentially of, or can be, a C₁₂ monoolefin, a C₁₆ monoolefin, a C₁₈monoolefin, or combinations thereof; alternatively, a C₁₂ monoolefin;alternatively, a C₁₆ monoolefin; or alternatively, a C₁₈ monoolefin.

In an embodiment, the first feedstock disclosed herein can furthercomprise C₈ monoolefins, C₁₂ monoolefins, C₁₆ monoolefins, C₁₈monoolefins, or combinations thereof; alternatively, C₈ monoolefins;alternatively, C₁₂ monoolefins; alternatively, C₁₆ monoolefins and/orC₁₈ monoolefins; alternatively, C₁₆ monoolefins; or alternatively, C₁₈monoolefins. In an embodiment, the C₈ monoolefins can comprise 1-octene.In an embodiment, the C₁₂ monoolefins can comprise 1-dodecene.

In an embodiment, the first feedstock can further comprise from about0.1 mol % to about 5 mol %, alternatively from about 0.25 mol % to about4 mol %, or alternatively from about 0.5 mol % to about 3 mol % C₁₂monoolefins. In such embodiment, the C₁₂ monoolefins can comprise fromabout 54 mol % to about 74 mol %, alternatively from about 56 mol % toabout 72 mol %, alternatively from about 58 mol % to about 70 mol %, oralternatively from about 60 mol % to about 68 mol % 1-dodecene.

In an embodiment, the first feedstock can further comprise from about0.1 mol % to about 5 mol %, alternatively from about 0.25 mol % to about4 mol %, or alternatively from about 0.5 mol % to about 3 mol % C₈monoolefins. In such embodiment, the C₈ monoolefins can comprise atleast about 95 mol %, alternatively at least about 96 mol %,alternatively at least about 97 mol %, alternatively at least about 98mol %, or alternatively at least about 99 mol % 1-octene.

In an embodiment, the first feedstock can further comprise from about0.05 mol % to about 2 mol %, alternatively from about 0.04 mol % toabout 1.5 mol %, alternatively from about 0.06 mol % to about 1.25 mol%, alternatively from about 0.08 mol % to about 1 mol %, oralternatively from about 0.1 mol % to about 0.75 mol % C₁₆ monoolefinsand/or C₁₈ monoolefins.

In an embodiment, a feedstock comprising branched C₁₀ monoolefinsproduced in a 1-hexene process can be purified to produce a secondfeedstock of the type described herein, for example to improve olefinreactivity and resultant mercaptan and/or sulfide purity. A lightfraction, comprising C⁹⁻, can be removed from the feedstock and any C₁₀olefin isomers can be collected overhead to obtain a high purity (>95%)C₁₀ monoolefin fraction as the second feedstock. This high purity C₁₀monoolefin fraction (i.e., second feedstock) comprises little or nonon-olefin impurities or C₁₁ to C₁₇ compounds. The high purity C₁₀olefin can be reacted with H₂S to produce a crude composition. Reactionconditions to produce a crude composition from the high purity C₁₀monoolefin fraction (i.e., a second feedstock) can be identical to thereaction conditions disclosed for the feedstock comprising branched C₁₀monoolefins produced in a 1-hexene process used as received withoutfurther purification (i.e., a first feedstock). The major differencebetween reacting a first feedstock and a second feedstock is thecomposition of the crude composition and any resulting purified orpartially purified products (e.g., fractions or cuts taken from thecrude composition). For the second feedstock (e.g., a high purity (>95%)C₁₀ monoolefin fraction), the crude composition can comprise residualH₂S, unreacted C₁₀ olefin, C₁₀ mercaptan isomers, and C₁₀H₂₁—S—C₁₀H₂₁sulfides and minimal other mercaptans or sulfides. After removal of H₂Sand C⁹⁻ lights from the crude composition, the resultant partiallypurified product will contain C₁₀ mercaptan isomers and C₂₀ sulfides,but will not contain any of the intermediate mercaptans and asymmetricsulfide components formed by reactions of olefins having less than orgreater than 10 carbon atoms (because there were minimal, if any, sucholefins having less than or greater than 10 carbon atoms in the purifiedfeedstock). While not wishing to be bound by theory, it is believed thatthe intermediate mercaptans and asymmetric sulfide components can beproduced from the reaction of C₁₀ mercaptans with other non-C₁₀ olefins.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted at an H₂S to olefin molar ratio of fromabout 1:1 to about 20:1, alternatively from about 2:1 to about 15:1, oralternatively from about 3:1 to about 10:1.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted at a pressure of from about 30 psig (206kPag) to about 1,500 psig (10,300 kPag), alternatively from about 100psig (690 kPag) to about 1,250 psig (8,600 kPag), or alternatively fromabout 250 psig (1,700 kPag) to about 1,000 psig (6,900 kPag).

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted to produce olefin conversion of equal toor greater than about 80%, alternatively equal to or greater than about85%, or alternatively equal to or greater than about 90%. For purposesof the disclosure herein, an olefin conversion refers to the mol % ofolefins that have reacted during the reaction between H₂S and afeedstock in a reactor, with respect to the amount of olefins introducedinto the reactor during the same time period.

In an embodiment, the process can comprise reacting H₂S and a feedstock(e.g., a first or second feedstock as described herein) comprising oneor more branched C₁₀ monoolefins in the presence of an initiating agentto produce a crude composition; wherein the initiating agent comprisesultraviolet (UV) radiation. In such embodiment, the UV radiation can beany UV radiation capable of initiating the reaction of the olefinspresent in the feedstock and H₂S. In some embodiments, the UV radiationcan be generated by a medium pressure mercury lamp. As will beappreciated by one of skill in the art, and with the help of thisdisclosure, although UV radiation can be the initiating agent, othersuitable types of light sources can be used.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an initiating agentcomprising UV radiation in a batch reactor or a continuous reactor.Nonlimiting examples of continuous reactors suitable for use in thepresent disclosure include continuous flow reactors, continuous stirredreactors, fixed bed reactors, and the like, or combinations thereof.Nonlimiting examples of batch reactors suitable for use in the presentdisclosure include UV batch reactors. As will be appreciated by one ofskill in the art, and with the help of this disclosure, any othersuitable type of batch and continuous reactors can be used for reactingH₂S and a feedstock comprising one or more branched C₁₀ monoolefins inthe presence of UV radiation. UV reactors and conditions suitable forreacting H₂S and a feedstock comprising one or more branched C₁₀monoolefins in the presence of UV radiation are described in more detailin U.S. Pat. No. 7,989,655, and U.S. Publication No. 20140221692 A1,each of which is incorporated by reference herein in its entirety.

In embodiments where H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins are reacted in the presence of UV radiation in acontinuous reactor, the continuous reactor can be sized and configuredto the desired continuous production rate. That is, a person skilled inthe art will be able to select an appropriate reaction vessel size,geometry and material (e.g., a transparent material for sidewalls,windows, or internal chambers); along with an appropriate number of UVsources; and arrange the sources and reactor vessel (e.g., place UVsources adjacent a transparent exterior portion of the reaction vesseland/or disposed in transparent chambers within the reactor vessel) toyield a desired continuous production rate.

In embodiments where H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins are reacted in the presence of UV radiation in a batchreactor, the batch reactor can be characterized by a reaction time offrom about 1 minute to about 4 hours, alternatively from about 10minutes to about 2 hours, or alternatively from about 30 minutes toabout 1.5 hours.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of UV radiation at atemperature of from about 0° C. to about 100° C., alternatively fromabout 10° C. to about 70° C., or alternatively from about 15° C. toabout 35° C.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of UV radiation at a H₂Sto olefin molar ratio of from about 1:1 to about 15:1, alternativelyfrom about 2:1 to about 12.5:1, or alternatively from about 5:1 to about10:1.

Multiple In an embodiment, the process can comprise reacting H₂S and afeedstock comprising one or more branched C₁₀ monoolefins in thepresence of an initiating agent to produce a crude composition; whereinthe initiating agent comprises ultraviolet (UV) radiation, and whereinthe initiating agent further comprises a phosphite promoter, aphotoinitiator, or both.

In an embodiment, the phosphite promoter can be used in an amount offrom about 0.01 wt. % to about 5 wt. %, alternatively from about 0.1 wt.% to about 4 wt. %, or alternatively from about 1 wt. % to about 2.5 wt.%, based on a weight of olefins.

In an embodiment, the phosphite promoter can be characterized by formulaP(OR⁵)₃, wherein each R⁵ can independently be a C₁-C₁₈ hydrocarbylgroup, alternatively C₁-C₁₀ hydrocarbyl group, alternatively C₁-C₅hydrocarbyl group; alternatively a C₁-C₁₈ alkyl group, alternativelyC₁-C₁₀ alkyl group, alternatively C₁-C₅ alkyl group; alternatively, aC₆-C₁₈ aryl group, or alternatively, a C₆-C₁₀ aryl group. Nonlimitingexamples of R⁵ groups suitable for use in the present disclosure in thephosphite promoter include a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group; a phenyl group, a tolylgroup, a xylyl group, a naphthyl group; and the like, or combinationsthereof.

Nonlimiting examples of phosphite promoters suitable for use in thepresent disclosure include a trialkylphosphite, trimethylphosphite,triethylphosphite, tributylphosphite; a triarylphosphite,triphenylphosphite; and the like, or combinations thereof.

In an embodiment, the photoinitiator can be used in an amount of fromabout 0.05 wt. % to about 5 wt. %, alternatively from about 0.1 wt. % toabout 4 wt. %, or alternatively from about 1 wt. % to about 2.5 wt. %,based on the weight of olefins present in the feed mixture.

Nonlimiting examples of photoinitiators suitable for use in the presentdisclosure include 1-hydroxy-cyclohexyl-phenyl-ketone, benzophenone,Bis-(2,4,6-trimethylbenzoyl)-phenylphosphineoxide,2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methy-1-propan-1-one,2-hydroxy-2-methyl-1-phenyl-1-propanone, and the like, or combinationsthereof.

In an embodiment, the process can comprise reacting H₂S and a feedstockcomprising one or more branched C₁₀ monoolefins in the presence of UVradiation to produce a crude composition (wherein the crude compositioncomprises from 50-100 wt. % C₁₀ mercaptans, alternatively from 50-90 wt.% C₁₀ mercaptans, alternatively from 75-85 wt. % C₁₀ mercaptans);wherein the C₁₀ mercaptans present in the crude composition furthercomprise from about 70 wt. % to about 100 wt. %, alternatively fromabout 70 wt. % to about 95 wt. %, alternatively from about 80 wt. % toabout 90 wt. %, or alternatively from about 79 wt. % to about 85 wt. %C₁₀ primary mercaptans; from about 0 wt. % to about 30 wt. %,alternatively from about 0 wt. % to about 20 wt. %, alternatively fromabout 10 wt. % to about 20 wt. %, or alternatively from about 5 wt. % toabout 19 wt. % C₁₀ secondary mercaptans; and from about 0 wt. % to about10 wt. %, alternatively from about 0 wt. % to about 5 wt. %, oralternatively from about 0 wt. % to about 3 wt. % C₁₀ tertiarymercaptans. For purposes of the disclosure herein, a primary mercaptanis a mercaptan that has the thiol group (—SH) attached to a primarycarbon (e.g., a carbon atom that is attached to one and only one othercarbon atom). Further, for purposes of the disclosure herein, asecondary mercaptan is a mercaptan that has the thiol group (—SH)attached to a secondary carbon (e.g., a carbon atom that is attached totwo and only two other carbon atoms). Further, for purposes of thedisclosure herein, a tertiary mercaptan is a mercaptan that has thethiol group (—SH) attached to a tertiary carbon (e.g., a carbon atomthat is attached to three and only three other carbon atoms). As will beappreciated by one of skill in the art, and with the help of thisdisclosure, the make-up of the crude composition, in terms of primary,secondary, and tertiary mercaptans, will depend on the make-up of thefeedstock, as well as on the reaction conditions. Further, as will beappreciated by one of skill in the art, and with the help of thisdisclosure, the make-up of each of the primary, secondary, and tertiarymercaptans will depend on the make-up of the feedstock, as well as onthe reaction conditions.

In an embodiment, the C₁₀ primary mercaptans can comprise5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),1-mercapto-decane (represented by Structure M), or combinations thereof.

In an embodiment, the C₁₀ secondary mercaptans can comprise4-mercapto-decane (represented by Structure N), 5-mercapto-decane(represented by Structure O), 5-methyl-2-mercapto-nonane (represented byStructure E), 3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),2-mercapto-decane (represented by Structure P), or combinations thereof.

In an embodiment, the C₁₀ tertiary mercaptans can comprise equal to orgreater than about 90 wt. %, alternatively equal to or greater thanabout 95 wt. %, or alternatively equal to or greater than about 99 wt. %5-methyl-5-mercapto-nonane (represented by Structure H).

In an embodiment, the process can comprise reacting H₂S and a feedstock(e.g., a first or second feedstock as described herein) comprising oneor more branched C₁₀ monoolefins in the presence of an initiating agent(e.g., catalyst) to produce a crude composition; wherein the initiatingagent comprises an acid catalyst. Nonlimiting examples of acid catalystssuitable for use in the present disclosure include acid washed clays(such as, but not limited to, Filtrol® 24 or Filtrol® 24X); acid washedbentonite; a tetrafluoroethylene polymer resin modified withperfluorovinyl ether groups terminated with sulfonate groups; amacroreticular, sulfonated, crosslinked copolymer of styrene and divinylbenzene; and the like, or combinations thereof.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an acid catalyst in acontinuous reactor, such as for example continuous flow reactor,continuous stirred reactors, fixed bed reactors, packed bed reactors,and the like, or combinations thereof.

In embodiments where H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins are reacted in the presence of an acid catalyst in acontinuous reactor, the continuous reactor can be characterized by aweight hourly space velocity (WHSV) of from about 0.1 h⁻¹ to about 5h⁻¹, alternatively from about 0.5 h⁻¹ to about 4 h⁻¹, or alternativelyfrom about 1 h⁻¹ to about 3 h⁻¹, based on mass of olefin per mass ofcatalyst per hour.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an acid catalyst at atemperature of from about 100° C. to about 300° C., alternatively fromabout 120° C. to about 220° C., or alternatively from about 180° C. toabout 200° C.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an acid catalyst at aH₂S to olefin molar ratio of from about 1:1 to about 10:1, alternativelyfrom about 2:1 to about 7.5:1, or alternatively from about 2.5:1 toabout 5:1.

In an embodiment, the process can comprise reacting H₂S and a feedstockcomprising one or more branched C₁₀ monoolefins in the presence of anacid catalyst to produce a crude composition (wherein the crudecomposition comprises from 50-100 wt. % C₁₀ mercaptans, alternativelyfrom 50-90 wt. % C₁₀ mercaptans, alternatively from 75-85 wt. % C₁₀mercaptans); wherein the C₁₀ mercaptans comprise from about 0 wt. % toabout 5 wt. % alternatively from about 0.1 wt. % to about 4 wt. %, oralternatively from about 0.5 wt. % to about 2.5 wt. % C₁₀ primarymercaptans; from about 80 wt. % to about 95 wt. %, alternatively fromabout 82.5 wt. % to about 92.5 wt. %, or alternatively from about 85 wt.% to about 90 wt. % C₁₀ secondary mercaptans; and from about 5 wt. % toabout 20 wt. %, alternatively from about 7.5 wt. % to about 17.5 wt. %,or alternatively from about 10 wt. % to about 15 wt. % C₁₀ tertiarymercaptans.

In an embodiment, the process can comprise reacting H₂S and a feedstock(e.g., a first or second feedstock as described herein) comprising oneor more branched C₁₀ monoolefins in the presence of an initiating agentto produce a crude composition; wherein the initiating agent comprises ahydrodesulfurization (HDS) catalyst.

In an embodiment, the HDS catalyst comprises a comprises a metal, atransition metal, Ru, Co, Mo, Ni, W, sulfides thereof, disulfidesthereof, and the like, or combinations thereof.

In an embodiment, the HDS catalyst can be Haldor Topsoe TK-554 orTK-570, and the like, or combinations thereof.

In an embodiment, the HDS catalyst can further comprise a support, suchas for example alumina, silica, and the like, or combinations thereof.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an HDS catalyst in acontinuous reactor, such as for example continuous flow reactor,continuous stirred reactors, fixed bed reactors, packed bed reactors,and the like, or combinations thereof.

In embodiments where H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins are reacted in the presence of an HDS catalyst in acontinuous reactor, the continuous reactor can be characterized by aWHSV of from about 0.1 h⁻¹ to about 5 h⁻¹, alternatively from about 0.5h⁻¹ to about 4 h⁻¹, or alternatively from about 1 h⁻¹ to about 3 h⁻¹,based on mass of olefin per mass of catalyst per hour.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an HDS catalyst at atemperature of from about 100° C. to about 300° C., alternatively fromabout 120° C. to about 220° C., or alternatively from about 180° C. toabout 200° C.

In an embodiment, H₂S and a feedstock comprising one or more branchedC₁₀ monoolefins can be reacted in the presence of an HDS catalyst at aH₂S to olefin molar ratio of from about 1:1 to about 10:1, alternativelyfrom about 2:1 to about 7.5:1, or alternatively from about 2.5:1 toabout 5:1.

In an embodiment, the process can comprise reacting H₂S and a feedstockcomprising one or more branched C₁₀ monoolefins in the presence of anHDS catalyst to produce a crude composition (wherein the crudecomposition comprises from 50-100 wt. % C₁₀ mercaptans, alternativelyfrom 50-90 wt. % C₁₀ mercaptans, alternatively from 75-85 wt. % C₁₀mercaptans); wherein the C₁₀ mercaptans comprise from about 5 wt. % toabout 30 wt. % alternatively from about 10 wt. % to about 25 wt. %, oralternatively from about 15 wt. % to about 20 wt. % C₁₀ primarymercaptans; from about 60 wt. % to about 75 wt. %, alternatively fromabout 62.5 wt. % to about 72.5 wt. %, or alternatively from about 65 wt.% to about 70 wt. % C₁₀ secondary mercaptans; and from about 5 wt. % toabout 15 wt. %, alternatively from about 7.5 wt. % to about 13.5 wt. %,or alternatively from about 9 wt. % to about 12 wt. % C₁₀ tertiarymercaptans.

As noted previously, any such feedstocks comprising one or more branchedC₁₀ monoolefins can be reacted with hydrogen sulfide (H₂S) in thepresence of an initiating agent to produce a crude composition, and thecrude composition can be further refined (e.g., distilled or otherwiseseparated into one or more fractions such as lights, intermediate, andheavies) to yield the various compositions described herein. Asdescribed in more detail herein, the type and/or amounts of theconstituent components that form the crude composition can varydepending upon the feedstock (e.g., the amount and types of olefinstherein), the reaction conditions, the catalysts employed, etc., and oneskilled in the art can tailor the post reactor processing of the crudecomposition to account for the specific compounds present in a givencrude composition to yield various desired products and compositions ofthe types described herein.

Upon completion of the reaction of a feedstock comprising one or morebranched C₁₀ monoolefins with hydrogen sulfide (H₂S), a reactor effluentcan be recovered from the reactor and H₂S removed therefrom to yield acrude composition. The term “crude composition” or “crude product”refers to an unrefined effluent stream recovered from the reactor afterremoval of H₂S, and in particular to an H₂S-free effluent stream thathas not undergone any additional post-reactor processing such asflashing, distillation, or other separation techniques or processes toremove any components from the effluent stream other than the initialremoval of H₂S.

Hydrogen sulfide (H₂S) is a highly corrosive, poisonous, flammable,explosive gas. As such, it is typically removed before the crudecomposition can be further processed or utilized. Bulk H₂S can beremoved under conditions of reduced pressure, and residual H₂S can beremoved at reduced temperature and pressure without removing anysubstantial quantities of the lights. Alternatively, H₂S can also beremoved by sparging inert gas into the liquid phase. Alternatively,there are other methods for removing H₂S (i.e., absorption, stripping,etc.) that are known to those of skill in the art. In an embodiment,under appropriate conditions, a reactor effluent can be treated toremove essentially all of any excess and/or unreacted hydrogen sulfide(H₂S).

The crude composition comprises branched C₁₀ mercaptans and branched C₂₀sulfides formed by the reaction of H₂S and the one or more branched C₁₀monoolefins, and the structures of these branched C₁₀ mercaptans andbranched C₂₀ sulfides are described in more detail herein. In additionto branched C₁₀ mercaptans and branched C₂₀ sulfides, the crudecomposition can comprise a number of other compounds such as unreactedolefins, inert compounds (e.g., alkanes), non-branched C₁₀ mercaptans,non-branched C₂₀ sulfides, non-C₁₀ mercaptans, non-C₂₀ sulfides, andother impurities. The constituent components contained within the crudecomposition can vary depending upon the composition of the feedstock(e.g., an unpurified first feedstock as compared to a purified secondfeedstock as described herein) as well as reaction conditions, catalyst,etc. In various embodiments, a crude composition can comprise light,intermediate, and heavy fractions as described herein.

In an embodiment, the crude compositions can contain a variety of othernon-C₁₀ mercaptan and non-C₂₀ sulfides components (e.g., impurities)such as C₈ mercaptans; C₁₂ mercaptans; C₁₄ mercaptans; C₁₆ mercaptans;C₁₈ mercaptans; C₁₆₋₃₆ sulfides represented by the structure R³—S—R⁴,wherein R³ and R⁴ are each independently a functional group derived froman olefin selected from the group consisting of C₈ monoolefins, C₁₀monoolefins, C₁₂ monoolefins, C₁₄ monoolefins, C₁₆ monoolefins, and C₁₈monoolefins, wherein R³ and R⁴ are not both branched C₁₀ monoolefins;unreacted C₈₋₁₈ monoolefins; non-olefin impurities selected from thegroup consisting of C₈₋₁₄ alkanes, cyclohexane, methylcyclopentane,methylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene,hexamethylbenzene, C₄₋₁₂ alcohols, 2-ethyl-1-hexanol, and2-ethylhexyl-2-ethylhexanoate; and combinations thereof.

In an embodiment, a crude composition comprising branched C₁₀ mercaptansand branched C₂₀ sulfides can be separated by any process or unitoperation known in the art. For example, a crude composition can beprocessed (e.g., distilled) to remove a fraction of light compounds.Alternatively, a crude composition can be processed to recover both alights fraction and an intermediates fraction (e.g., a rough cut),followed by further processing to obtain one or more fine cuts.Alternatively, a crude composition can be processed to recover a heaviesfraction (e.g., a C₂₀ sulfide fraction). Alternatively, a crudecomposition can be processed to separate out any combination of a lightsfraction, an intermediates fraction (e.g., comprising C₁₀ mercaptans,including branched C₁₀ mercaptans), and a heavies fraction (e.g.,comprising C₂₀ sulfides, including branched C₂₀ sulfides). Furthermore,a light, intermediate or heavy fraction (e.g., a rough cut) can befurther processed or parsed to obtain one or more desired fine cuts(e.g., a C₁₀ mercaptan fraction). Alternatively, a crude composition canbe separated to produce a high-purity C₁₀ mercaptan stream and/or ahigh-purity C₂₀ sulfide stream (e.g., to obtain a desired fine cut orfraction such as a C₁₀ mercaptan fraction). Further, these separatedstreams can be blended in any combination of ratios to produce a mixturewith specific concentrations of one of more components (e.g., desiredblend ratios of branched C₁₀ mercaptans and/or branched C₂₀ sulfides,for example to aid in a particular end use). The unitoperations/processes used for these separations are known to one ofskill and the art and include, but are not limited to, distillation,fractionation, flashing, stripping, and absorption, and others. The unitoperation conditions, such as for example, temperature, pressure, flowrates, and others at which these unit operations produce one or more ofthe desired fractions can easily be determined by one of ordinary skillin the art.

In an embodiment, a lights fraction is removed from the crudecomposition, for example by flashing, distillation, fractionation,stripping, absorption, etc.

In an embodiment, the lights fraction can comprise at least about 90 wt.%, alternatively at least about 90 wt. %, alternatively at least about95 wt. %, alternatively at least about 96 wt. %, alternatively at leastabout 97 wt. %, alternatively at least about 98 wt. %, alternatively atleast about 99 wt. % C⁹⁻ compounds, based on the total weight of thelights fraction. Nonlimiting examples of C⁹⁻ compounds include C⁹⁻monoolefins (e.g., unreacted C⁹⁻ monoolefins), C⁹⁻ mercaptans, C⁹⁻alkanes, cyclohexane, methylcyclopentane, methylcyclohexane, benzene,toluene, ethylbenzene, xylene, mesitylene, C⁹⁻ alcohols,2-ethyl-1-hexanol, and the like, or combinations thereof. In anembodiment, the lights fraction can comprise less than about 10 wt. %,alternatively less than about 5 wt. %, alternatively less than about 4wt. %, alternatively at less than about 3 wt. %, alternatively less thanabout 2 wt. %, alternatively less than about 1 wt. % C₁₀₊ compounds,based on the total weight of the lights fraction.

In an embodiment, the C⁹⁻ monoolefins can comprise, can consistessentially of, or can be, a C₇ monoolefin, a C₈ monoolefin, a C₉monoolefin, or combinations thereof; alternatively, a C₇ monoolefin;alternatively, a C₈ monoolefin; or alternatively, a C₉ monoolefin. Insome embodiments, the C⁹⁻ monoolefins can comprise, can consistessentially of, or can be, a C₈ monoolefin (e.g., 1-octene).

In an embodiment, the C⁹⁻ mercaptans can comprise, can consistessentially of, or can be, a C₇ mercaptan, a C₈ mercaptan, a C₉mercaptan, or combinations thereof; alternatively, a C₇ mercaptan;alternatively, a C₈ mercaptan; or alternatively, a C₉ mercaptan. In someembodiments, the C⁹⁻ mercaptans can comprise, can consist essentiallyof, or can be, a C₈ mercaptan.

Following removal of the lights (for example, via flash), a combinedintermediate and heavy fraction (i.e., C₁₀₊ compounds sometimes referredto as a kettle product in the Examples) can remain, and the combinedintermediate and heavy fraction can be used “as is” or can be furtherprocessed, for example separated or split into separate intermediate andheavy fractions (and said separate intermediate and heavy fractions canbe subsequently recombined in various blends and associated blendratios), as described in more detail herein. In an embodiment, acombined intermediate and heavy fraction (i.e., C₁₀₊ compounds) formedby removal of the lights fraction from the crude composition cancomprise less than about 15 wt. %, alternatively less than about 10 wt.%, alternatively less than about 9 wt. %, alternatively less than about8 wt. %, alternatively less than about 7 wt. %, alternatively less thanabout 6 wt. %, alternatively less than about 5 wt. %, alternatively lessthan about 4 wt. %, alternatively less than about 3 wt. %, alternativelyless than about 2 wt. %, alternatively less than about 1 wt. % C⁹⁻products, based on the total weight of the combined intermediate andheavy fraction (i.e., C₁₀₊ compounds).

In an embodiment, a combined intermediate and heavy fraction (i.e., C₁₀₊compounds) can comprise (A) at least about 50 wt. %, alternatively atleast about 60 wt. %, alternatively at least about 70 wt. %,alternatively at least about 80 wt. %, alternatively at least about 90wt. %, alternatively at least about 95 wt. %, or alternatively at leastabout 99 wt. % mercaptans; wherein at least about 50 wt. %,alternatively at least about 60 wt. %, alternatively at least about 70wt. %, alternatively at least about 75 wt. %, alternatively at leastabout 80 wt. %, or alternatively at least about 85 wt. % of themercaptans can be branched C₁₀ mercaptans selected from the groupconsisting of 5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; and (B) at least about 10 wt. %, alternatively atleast about 15 wt. %, alternatively at least about 20 wt. %,alternatively at least about 25 wt. % sulfides, or alternatively atleast about 30 wt. % sulfides; wherein at least about 50 wt. %,alternatively at least about 60 wt. %, alternatively at least about 70wt. %, alternatively at least about 75 wt. %, alternatively at leastabout 80 wt. %, or alternatively at least about 85 wt. % of the sulfidescan be branched C₂₀ sulfides represented by structure R¹—S—R², whereinboth R¹ and R² can each independently be a functional group derived froman olefin, wherein the olefin comprises 5-methyl-1-nonene (representedby Structure I), 3-propyl-1-heptene (represented by Structure J),4-ethyl-1-octene (represented by Structure K), 2-butyl-1-hexene(represented by Structure L), or combinations thereof.

In an embodiment, the crude composition can be flashed to remove alights fraction as described herein to produce a combined intermediateand heavy fraction (i.e., C₁₀₊ compounds) comprising: (A) at least about25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt. % C₁₀ branchedmercaptans selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; and (B) at least about 5 wt. %, alternatively atleast about 10 wt. %, alternatively at least about 15 wt. %,alternatively at least about 20 wt. %, alternatively at least about 25wt. %, or alternatively at least about 30 wt. % branched C₂₀ sulfidesrepresented by structure R¹—S—R², wherein both R¹ and R² can eachindependently be a functional group derived from an olefin, wherein theolefin comprises 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof.

In an embodiment, the crude composition can be flashed to remove alights fraction as described herein to produce a combined intermediateand heavy fraction (i.e., C₁₀₊ compounds) comprising: (A) from at leastabout 50 wt. % to at least about 90 wt. %, alternatively from at leastabout 55 wt. % to at least about 85 wt. %, or alternatively from atleast about 60 wt. % to at least about 80 wt. % mercaptans, wherein atleast about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at leastabout 85 wt. % of the mercaptans can be branched C₁₀ mercaptans selectedfrom the group consisting of 5-methyl-1-mercapto-nonane (represented byStructure A), 3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; and (B) from at least about 10 wt. % to at leastabout 30 wt. %, alternatively from at least about 10 wt. % to at leastabout 25 wt. %, alternatively from at least about 12.5 wt. % to at leastabout 22.5 wt. %, or alternatively from at least about 15 wt. % to atleast about 20 wt. % sulfides; wherein at least about 50 wt. %,alternatively at least about 60 wt. %, alternatively at least about 70wt. %, alternatively at least about 75 wt. %, alternatively at leastabout 80 wt. %, or alternatively at least about 85 wt. % of the sulfidescan be branched C₂₀ sulfides represented by structure R¹—S—R², whereinboth R¹ and R² can each independently be a functional group derived froman olefin, wherein the olefin comprises 5-methyl-1-nonene (representedby Structure I), 3-propyl-1-heptene (represented by Structure J),4-ethyl-1-octene (represented by Structure K), 2-butyl-1-hexene(represented by Structure L), or combinations thereof.

In an embodiment, the crude composition can be flashed to remove alights fraction and subsequently further separated to produce anintermediate fraction and a heavies fraction. The intermediate fractionand the heavies fractions can then be optionally further processed(e.g., polished) and mixed in any appropriate ratio to produce a blendedcomposition comprising: (A) at least about 25 wt. %, alternatively atleast about 30 wt. %, alternatively at least about 40 wt. %,alternatively at least about 50 wt. %, alternatively at least about 80wt. %, or alternatively at least about 90 wt. % C₁₀ mercaptans (e.g.,branched C₁₀ mercaptans) selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; (B) at least about 5 wt. %, alternatively at leastabout 10 wt. %, alternatively at least about 15 wt. %, alternatively atleast about 20 wt. %, alternatively at least about 25 wt. %, oralternatively at least about 30 wt. % C₂₀ sulfides (e.g., branched C₂₀sulfides) represented by structure R¹—S—R², wherein R¹ and R² can eachindependently be a functional group derived from an olefin, wherein theolefin comprises 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof; and one or more of the following components(C)-(I): (C) less than about 5 wt. %, alternatively less than about 4wt. %, alternatively less than about 3 wt. %, alternatively less thanabout 2 wt. %, or alternatively less than about 1 wt. % C₈ mercaptans;(D) less than about 15 wt. %, alternatively less than about 10 wt. %, oralternatively less than about 5 wt. % C₁₂ mercaptans; (E) less thanabout 15 wt. %, alternatively less than about 10 wt. %, or alternativelyless than about 5 wt. % C₁₄ mercaptans; (F) less than about 5 wt. %,alternatively less than about 4 wt. %, alternatively less than about 3wt. %, alternatively less than about 2 wt. %, or alternatively less thanabout 1 wt. % C₁₆ mercaptans and/or C₁₈ mercaptans; (G) less than about1 wt. %, alternatively less than about 0.5 wt. %, alternatively lessthan about 0.4 wt. %, alternatively less than about 0.3 wt. %,alternatively less than about 0.2 wt. %, or alternatively less thanabout 0.1 wt. % C₁₆₋₃₆ sulfides represented by the structure R³—S—R⁴,wherein R³ and R⁴ are each independently a functional group derived froman olefin selected from the group consisting of C₈ monoolefins, C₁₀monoolefins, C₁₂ monoolefins, C₁₄ monoolefins, C₁₆ monoolefins, and C₁₈monoolefins, wherein R³ and R⁴ are not both branched C₁₀ monoolefins;(H) less than about 10 wt. %, alternatively less than about 5 wt. %,alternatively less than about 4 wt. %, alternatively less than about 3wt. %, alternatively less than about 2 wt. %, or alternatively less thanabout 1 wt. % unreacted C₈₋₁₈ monoolefins; and (I) less than about 10wt. %, alternatively less than about 5 wt. %, alternatively less thanabout 4 wt. %, alternatively less than about 3 wt. %, alternatively lessthan about 2 wt. %, or alternatively less than about 1 wt. % non-olefinimpurities selected from the group consisting of C₈₋₁₄ alkanes,cyclohexane, methylcyclopentane, methylcyclohexane, benzene, toluene,ethylbenzene, xylene, mesitylene, hexamethylbenzene, C₄₋₁₂ alcohols,2-ethyl-1-hexanol, and 2-ethylhexyl-2-ethylhexanoate. In variousembodiments, the blended composition can comprise varying amounts ofeach of components (C)-(I), and the presence of each component (C)-(I)and the amount thereof can be independently formulated and/orcontrolled. In various embodiments, the blended composition can comprisean amount of one or more components (C)-(I) that is greater than zero(i.e., above a detection limit associated with the component) and lessthan the upper range endpoint set forth above (e.g., component (C) ispresent in the composition in an amount greater than zero and less thanabout 5 wt. %, and so forth as set forth above).

In some embodiments, a mercaptan/sulfide composition of the typedisclosed herein can be prepared by combining at least a portion of afirst mercaptan/sulfide composition (wherein only a lights fraction hasbeen removed from the crude product to yield a combined intermediate andheavy fraction, e.g., C₁₀₊ compounds) with at least a portion of aheavies fraction comprising a sulfide composition to yield a secondmercaptan/sulfide composition, wherein a sulfide content of the secondmercaptan/sulfide composition is greater than a sulfide content of thefirst mercaptan/sulfide composition.

In an embodiment, the crude can be separated into light, intermediate,and heavy fractions by distillation, for example in a singledistillation column having a light fraction recovered as an overheadstream, an intermediate fraction (e.g., comprising branched C₁₀mercaptans) recovered as a side stream, and a heavy fraction (e.g.,comprising branched C₂₀ sulfides) recovered as a bottom stream. Inalternative embodiments, the separation can be in sequential steps suchas removal of the lights fraction in a first distillation column,followed by separation of the intermediate fraction (e.g., comprisingbranched C₁₀ mercaptans) as an overhead stream in a second distillationcolumn and the heavy fraction (e.g., comprising C₁₁₊ compounds,including branched C₂₀ sulfides) as a bottom stream of the seconddistillation column. These “rough-cut” light, intermediate, and heavystreams can be used “as is” or they can be further processed (e.g.,further refined or polished, for example by additional distillation orother separation techniques to produce “fine-cuts”) and/or blended toobtain a variety of products that are salable or otherwise available fora variety of end uses such as mining ore collector compositions or chaintransfer agents. For example, a variety of mercaptan compositions,sulfide compositions, and mixed mercaptan/sulfide compositions can beproduced of the type disclosed in more detail herein.

In an embodiment, an intermediate fraction can comprise at least about25 wt. %, alternatively at least about 30 wt. %, alternatively at leastabout 40 wt. %, alternatively at least about 50 wt. % branched C₁₀mercaptans, alternatively at least about 75 wt. % branched C₁₀mercaptans, or alternatively at least about 85 wt. % branched C₁₀mercaptans. In such embodiment, the branched C₁₀ mercaptans can beselected from the group consisting of 5-methyl-1-mercapto-nonane(represented by Structure A), 3-propyl-1-mercapto-heptane (representedby Structure B), 4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In an embodiment, the heavy fraction can comprise at least about 5, 10,15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt. %,branched C₂₀ sulfides represented by structure R¹—S—R², wherein both R¹and R² are each independently a branched C₁₀ alkyl group derived fromthe branched C₁₀ monoolefin, and wherein the branched C₁₀ alkyl group isselected from the group consisting of

wherein * designates the attachment point to the S atom of the branchedC₂₀ sulfide.

In an embodiment, a mercaptan composition can comprise mercaptans,wherein at least a portion of the mercaptans comprise C₁₀ mercaptans,and wherein at least a portion of the C₁₀ mercaptans comprise branchedC₁₀ mercaptans. In an embodiment, the branched C₁₀ mercaptans cancomprise 5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), or combinationsthereof.

For purposes of the disclosure herein, branched C₁₀ mercaptans refer tomercaptans (or thiols) that are characterized by the general formulaR—SH, wherein R is a branched alkyl group (as opposed to a linear alkylgroup), i.e., an alkyl group substituted with alkyl substituents; andwherein R has a total of 10 carbon atoms. Further, for purposes of thedisclosure herein, a composition comprising mercaptans, wherein at leasta portion of the mercaptans are branched C₁₀ mercaptans (e.g.,5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), or combinationsthereof), can also be referred to as a “branched C₁₀ mercaptancomposition.” In an embodiment, the mercaptan composition can compriseany suitable amount of branched C₁₀ mercaptans.

In an embodiment, the C₁₀ mercaptans can further comprise non-branchedC₁₀ mercaptans, such as for example 1-mercapto-decane (represented byStructure M), 4-mercapto-decane (represented by Structure N),5-mercapto-decane (represented by Structure O), 2-mercapto-decane(represented by Structure P), or combinations thereof.

In some embodiments, a mercaptan composition can comprise mercaptans,wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 80wt. %, alternatively at least about 90 wt. %, alternatively at leastabout 95 wt. %, or alternatively at least about 99 wt. % of themercaptans can be branched C₁₀ mercaptans selected from the groupconsisting of 5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In other embodiments, a mercaptan composition can comprise at leastabout 1 wt. %, alternatively at least about 5 wt. %, alternatively atleast about 10 wt. %, alternatively at least about 20 wt. %,alternatively at least about 30 wt. %, alternatively at least about 40wt. %, alternatively at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 80 wt. %, alternatively at least about 90 wt. %,alternatively at least about 95 wt. %, or alternatively at least about99 wt. % mercaptans, wherein at least a portion of the mercaptans can bebranched C₁₀ mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In yet other embodiments, a mercaptan composition can comprise at leastabout 50 wt. %, alternatively at least about 60 wt. %, alternatively atleast about 70 wt. %, alternatively at least about 80 wt. %,alternatively at least about 90 wt. %, alternatively at least about 95wt. %, or alternatively at least about 99 wt. % mercaptans; wherein atleast about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at least85 wt. % of the mercaptans can be branched C₁₀ mercaptans selected fromthe group consisting of 5-methyl-1-mercapto-nonane (represented byStructure A), 3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In yet other embodiments, a mercaptan composition can comprise at leastabout 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt. % mercaptans;wherein at least about 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,85, 90, 95, or 99 wt. % of the mercaptans can be branched C₁₀ mercaptansselected from the group consisting of 5-methyl-1-mercapto-nonane(represented by Structure A), 3-propyl-1-mercapto-heptane (representedby Structure B), 4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In still yet other embodiments, a mercaptan composition can comprisefrom at least about 50 wt. % to at least about 90 wt. %, alternativelyfrom at least about 55 wt. % to at least about 85 wt. %, oralternatively from at least about 60 wt. % to at least about 80 wt. %mercaptans, wherein at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 75 wt. %, alternatively at least about 80 wt. %, oralternatively at least about 85 wt. % of the mercaptans can be branchedC₁₀ mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In still yet other embodiments, a mercaptan composition can consist ofor consist essentially of branched C₁₀ mercaptans selected from thegroup consisting of 5-methyl-1-mercapto-nonane (represented by StructureA), 3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In still yet other embodiments, a mercaptan composition can comprise atleast about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,75, 80, 85, 90, 95, or 99 wt. % branched C₁₀ mercaptans selected fromthe group consisting of 5-methyl-1-mercapto-nonane (represented byStructure A), 3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In still yet other embodiments, a composition can comprise mercaptans,wherein at least about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.% of the mercaptans are branched C₁₀ mercaptans selected from the groupconsisting of 5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof.

In an embodiment, a sulfide composition can comprise sulfides, whereinat least a portion of the sulfides comprise C₂₀ sulfides, and wherein atleast a portion of the C₂₀ sulfides comprise branched C₂₀ sulfidesrepresented by structure R¹—S—R², wherein R¹ and R² can eachindependently be an alkyl group, and wherein at least a portion of thealkyl groups comprises a branched C₁₀ alkyl group. In an embodiment, thealkyl group (e.g., a branched C₁₀ alkyl group as R¹, R²) can comprise afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

For purposes of the disclosure herein a sulfide will be referred to bythe total number of carbon atoms (as opposed to the number of carbons ofonly one of the alkyl groups present in a dialkyl sulfide). For example,a H₂₁C₁₀—S—C₁₀H₂₁ sulfide will be referred to as a C₂₀ sulfide (ratherthan a C₁₀ sulfide). For purposes of the disclosure herein, branched C₂₀sulfides refer to sulfides (or thioethers) that are characterized by thegeneral formula R¹—S—R², wherein both R¹ and R² are each independently abranched C₁₀ alkyl group (as opposed to a linear alkyl group), i.e., analkyl group substituted with alkyl substituents. Stated alternatively,branched C₂₀ sulfides refer to sulfides wherein both R¹ and R² arebranched C₁₀ alkyl groups, wherein R¹ and R² can be the same ordifferent. Further, for purposes of the disclosure herein, a compositioncomprising sulfides, wherein at least a portion of the sulfides arebranched C₂₀ sulfides represented by structure R¹—S—R², wherein both R¹and R² are each independently an alkyl group, wherein at least a portionof the alkyl group comprises a branched C₁₀ alkyl group (e.g., afunctional group derived from an olefin, and wherein the olefincomprises 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof), can also be referred to as a “branched C₂₀sulfide composition.” In an embodiment, the sulfide composition cancomprise any suitable amount of branched C₂₀ sulfides.

In an embodiment, a sulfide composition can comprise sulfides, whereinat least a portion of the sulfides comprise C₂₀ sulfides, and wherein atleast a portion of the C₂₀ sulfides comprise branched C₂₀ sulfidesrepresented by structure R¹—S—R², wherein both R¹ and R² can eachindependently be a branched C₁₀ alkyl group derived from a branched C₁₀monoolefin, and wherein the branched C₁₀ alkyl group is selected fromthe group consisting of

wherein * designates the attachment point to the S atom of the branchedC₂₀ sulfide. In an embodiment, the branched C₁₀ monoolefin can comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof. Generally, a monoolefin is a linear or branched aliphatichydrocarbon olefin that has one and only one carbon-carbon double bond.Generally, a C_(n) monoolefin is a linear or branched aliphatichydrocarbon olefin that has n and only n carbon atoms, and one and onlyone carbon-carbon double bond. A C₁₀ monoolefin is a linear or branchedaliphatic hydrocarbon olefin that has ten and only ten carbon atoms, andone and only one carbon-carbon double bond. A branched C₁₀ monoolefin isa branched aliphatic hydrocarbon olefin that has ten and only ten carbonatoms, and one and only one carbon-carbon double bond.

In an embodiment, the C₂₀ sulfides can further comprise non-branched C₂₀sulfides and/or partially branched C₂₀ sulfides represented by structureR¹—S—R², wherein both R¹ and R² (in the case of non-branched C₂₀sulfides) or one of the R¹ and R² (in the case of partially-branched C₂₀sulfides) can be a linear C₁₀ alkyl group derived from a linear C₁₀monoolefin, such as for example 4-decene (represented by Structure Q),5-decene (represented by Structure R), 1-decene (represented byStructure S), or combinations thereof.

For purposes of the disclosure herein, the non-branched C₂₀ sulfidesrepresented by structure R¹—S—R² are the sulfides wherein both R¹ and R²are each independently a linear C₁₀ alkyl group derived from a linearC₁₀ monoolefin. Further, for purposes of the disclosure herein, thepartially branched C₂₀ sulfides represented by structure R¹—S—R² are thesulfides wherein one of the R¹ and R² is a linear C₁₀ alkyl groupderived from a linear C₁₀ monoolefin, while the other one of the R¹ andR² is a branched C₁₀ alkyl group derived from a branched C₁₀ monoolefinas described herein.

In some embodiments, a sulfide composition can comprise sulfides,wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 80wt. %, alternatively at least about 90 wt. %, alternatively at leastabout 95 wt. %, or alternatively at least about 99 wt. % of the sulfidescan be branched C₂₀ sulfides represented by structure R¹—S—R², whereinboth R¹ and R² can each independently be a functional group derived froman olefin, wherein the olefin comprises 5-methyl-1-nonene (representedby Structure I), 3-propyl-1-heptene (represented by Structure J),4-ethyl-1-octene (represented by Structure K), 2-butyl-1-hexene(represented by Structure L), or combinations thereof.

In other embodiments, a sulfide composition can comprise at least about1 wt. %, alternatively at least about 5 wt. %, alternatively at leastabout 10 wt. %, alternatively at least about 20 wt. %, alternatively atleast about 30 wt. %, alternatively at least about 40 wt. %,alternatively at least about 50 wt. %, alternatively at least about 60wt. %, alternatively at least about 70 wt. %, alternatively at leastabout 80 wt. %, alternatively at least about 90 wt. %, alternatively atleast about 95 wt. %, or alternatively at least about 99 wt. % sulfides,wherein at least a portion of the sulfides can be branched C₂₀ sulfidesrepresented by structure R¹—S—R², wherein both R¹ and R² can eachindependently be a functional group derived from an olefin, wherein theolefin comprises 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof.

In other embodiments, a sulfide composition can comprise at least about1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85,90, 95, or 99 wt. %, sulfides, wherein at least about 1, 5, 10, 15, 20,25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt. %of the sulfides can be branched C₂₀ sulfides represented by structureR¹—S—R², wherein both R¹ and R² can each independently be a functionalgroup derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In yet other embodiments, a sulfide composition can comprise at leastabout 10 wt. %, alternatively at least about 15 wt. %, alternatively atleast about 20 wt. %, or alternatively at least about 25 wt. % sulfides;wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at leastabout 85 wt. % of the sulfides can be branched C₂₀ sulfides representedby structure R¹—S—R², wherein both R¹ and R² can each independently be afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In still yet other embodiments, a sulfide composition can comprise fromat least about 10 wt. % to at least about 30 wt. %, alternatively fromat least about 12.5 wt. % to at least about 22.5 wt. %, or alternativelyfrom at least about 15 wt. % to at least about 20 wt. % sulfides;wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at leastabout 85 wt. % of the sulfides can be branched C₂₀ sulfides representedby structure R¹—S—R², wherein both R¹ and R² can each independently be afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In still yet other embodiments, a sulfide composition can consist of orconsist essentially of branched C₂₀ sulfides represented by structureR¹—S—R², wherein both R¹ and R² can each independently be a functionalgroup derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In still yet other embodiments, a sulfide composition can comprise atleast about 5 wt. %, alternatively at least about 10 wt. %,alternatively at least about 15 wt. %, or alternatively at least about20 wt. % C₂₀ sulfides (e.g., branched C₂₀ sulfides) represented bystructure R¹—S—R², wherein both R¹ and R² can each independently be afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In still yet other embodiments, a sulfide composition comprises at leastabout 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,85, 90, 95, or 99 wt. % branched C₂₀ sulfides represented by thestructure R¹—S—R², wherein R¹ and R² are each independently a functionalgroup derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In an embodiment, a mercaptan/sulfide composition can comprise one ormore mercaptans and one or more sulfides of the type disclosed herein.For purposes of the disclosure herein, a composition comprising (i)mercaptans, wherein at least a portion of the mercaptans are branchedC₁₀ mercaptans, and (ii) sulfides, wherein at least a portion of thesulfides are branched C₂₀ sulfides, can also be referred to as a“branched C₁₀ mercaptan/C₂₀ sulfide composition.” In an embodiment, themercaptan/sulfide composition can comprise any suitable amount ofbranched C₁₀ mercaptans, and any suitable amount of branched C₂₀sulfides.

In an embodiment, a mercaptan/sulfide composition can comprise (A) atleast about 1 wt. %, alternatively at least about 5 wt. %, alternativelyat least about 10 wt. %, alternatively at least about 20 wt. %,alternatively at least about 30 wt. %, alternatively at least about 40wt. %, alternatively at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 80 wt. %, alternatively at least about 90 wt. %,alternatively at least about 95 wt. %, or alternatively at least about99 wt. % mercaptans, wherein at least a portion of the mercaptans can bebranched C₁₀ mercaptans selected from the group consisting of5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), andcombinations thereof; and (B) at least about 1 wt. %, alternatively atleast about 5 wt. %, alternatively at least about 10 wt. %,alternatively at least about 20 wt. %, alternatively at least about 30wt. %, alternatively at least about 40 wt. %, alternatively at leastabout 50 wt. %, alternatively at least about 60 wt. %, alternatively atleast about 70 wt. %, alternatively at least about 80 wt. %,alternatively at least about 90 wt. %, alternatively at least about 95wt. %, or alternatively at least about 99 wt. % sulfides, wherein atleast a portion of the sulfides can be branched C₂₀ sulfides representedby structure R¹—S—R², wherein both R¹ and R² can each independently be afunctional group derived from an olefin, wherein the olefin comprises5-methyl-1-nonene (represented by Structure I), 3-propyl-1-heptene(represented by Structure J), 4-ethyl-1-octene (represented by StructureK), 2-butyl-1-hexene (represented by Structure L), or combinationsthereof.

In an embodiment, a mercaptan/sulfide composition can comprise C₁₀mercaptans represented by the general formula R—SH and/or C₂₀ sulfidesrepresented by structure R¹—S—R² that are formed by reacting an olefinfeedstock comprising olefins with H₂S as described in more detailherein, wherein the olefins present in the olefin feedstock provide thealkyl group represented by R, R¹, and R². In such embodiments, the Rgroup of the C₁₀ mercaptans and/or the R¹ and R² groups of the C₂₀sulfides are provided by or derived from the counterpart R, R¹, and R²groups present in the olefins in the olefin feedstock. In an embodiment,R, R¹ and R² can each independently be an alkyl group, wherein at leasta portion of the alkyl groups can comprise a functional group derivedfrom an olefin, wherein the olefin is present in a feedstock (e.g., afirst feedstock as described herein) comprising a) at least about 76 mol%, alternatively at least about 78 mol %, alternatively at least about80 mol %, or alternatively at least about 82 mol % C₁₀ monoolefins; andb) at least about 1 mol %, alternatively at least about 2 mol %,alternatively at least about 3 mol %, or alternatively at least about 4mol % C₁₄ monoolefins. In such embodiment, the C₁₀ monoolefins cancomprise i) at least about 3 mol %, alternatively at least about 4 mol%, alternatively at least about 5 mol %, alternatively at least about 6mol %, alternatively at least about 7 mol %, or alternatively at leastabout 8 mol % 2-butyl-1-hexene (represented by Structure L), ii) atleast about 8 mol %, alternatively at least about 9 mol %, alternativelyat least about 10 mol %, alternatively at least about 11 mol %,alternatively at least about 12 mol %, or alternatively at least about13 mol % 3-propyl-1-heptene (represented by Structure J), iii) at leastabout 6 mol %, alternatively at least about 7 mol %, alternatively atleast about 8 mol %, alternatively at least about 9 mol %, alternativelyat least about 10 mol %, or alternatively at least about 11 mol %4-ethyl-1-octene (represented by Structure K), and iv) at least about 20mol %, alternatively at least about 22 mol %, alternatively at leastabout 24 mol %, alternatively at least about 26 mol %, alternatively atleast about 28 mol %, or alternatively at least about 30 mol %5-methyl-1-nonene (represented by Structure I). In an embodiment, theC₁₀ monoolefins can comprise from about 1 mol % to about 16 mol %,alternatively from about 2 mol % to about 15 mol %, alternatively fromabout 3 mol % to about 14 mol %, alternatively from about 4 mol % toabout 13 mol %, or alternatively from about 6 mol % to about 12 mol %4-decene and/or 5-decene. In an embodiment, the C₁₀ monoolefins cancomprise from about 0.5 mol % to about 9 mol %, alternatively from about1 mol % to about 8 mol %, alternatively from about 1.5 mol % to about 7mol %, or alternatively from about 2 mol % to about 6 mol % 1-decene.

In an embodiment, the olefin (e.g., corresponding to R, R¹ or R²)present in the olefin feedstock (e.g., a first feedstock as describedherein) can further comprise from about 0.1 mol % to about 5 mol %,alternatively from about 0.25 mol % to about 4 mol %, or alternativelyfrom about 0.5 mol % to about 3 mol % C₁₂ monoolefins. In suchembodiment, the C₁₂ monoolefins can comprise from about 54 mol % toabout 74 mol %, alternatively from about 56 mol % to about 72 mol %,alternatively from about 58 mol % to about 70 mol %, or alternativelyfrom about 60 mol % to about 68 mol % 1-dodecene.

In an embodiment, the olefin (e.g., corresponding to R, R¹ or R²)present in the olefin feedstock (e.g., a first feedstock as describedherein) can further comprise from about 0.1 mol % to about 5 mol %,alternatively from about 0.25 mol % to about 4 mol %, or alternativelyfrom about 0.5 mol % to about 3 mol % C₈ monoolefins. In suchembodiment, the C₈ monoolefins can comprise at least about 95 mol %,alternatively at least about 96 mol %, alternatively at least about 97mol %, alternatively at least about 98 mol %, or alternatively at leastabout 99 mol % 1-octene.

In an embodiment, the olefin (e.g., corresponding to R, R¹ or R²)present in the olefin feedstock (e.g., a first feedstock as describedherein) can further comprise from about 0.05 mol % to about 2 mol %,alternatively from about 0.04 mol % to about 1.5 mol %, alternativelyfrom about 0.06 mol % to about 1.25 mol %, alternatively from about 0.08mol % to about 1 mol %, or alternatively from about 0.1 mol % to about0.75 mol % C₁₆ monoolefins and/or C₁₈ monoolefins.

In an embodiment where the R group of the C₁₀ mercaptans and/or the R¹and R² groups of the C₂₀ sulfides are provided by or derived from thecounterpart R, R¹, and R² groups present in the olefins in the olefinfeedstock (e.g., a first feedstock obtained from a 1-hexene process asdescribed herein), the resultant mercaptan/sulfide composition can be acrude composition that can be further separated and refined into othercompositions as described herein.

In an embodiment, mercaptan compositions, sulfide compositions, and/ormercaptan/sulfide compositions as disclosed herein advantageouslydisplay improvements in one or more composition characteristics whencompared to otherwise similar compositions lacking branched C₁₀mercaptans.

In an embodiment, a mercaptan composition and/or a mercaptan/sulfidecomposition comprising equal to or greater than about 25 wt. % C₁₀branched mercaptans as disclosed herein can advantageously have an odorless unpleasant and less offensive than an odor of an otherwise similarcomposition comprising equal to or greater than about 25 wt. % n-decylmercaptan, as perceived by equal to or greater than about 51% of humansubjects exposed to the odor of each composition.

In an embodiment, a mercaptan composition and/or a mercaptan/sulfidecomposition comprising equal to or greater than about 25 wt. % C₁₀branched mercaptans as disclosed herein can advantageously have an odorless unpleasant than an odor of an otherwise similar compositioncomprising equal to or greater than about 25 wt. % n-dodecyl mercaptanand/or tert-dodecyl mercaptan, as perceived by equal to or greater thanabout 51% of human subjects exposed to the odor of each composition.Additional advantages of the mercaptan compositions, sulfidecompositions, and/or mercaptan/sulfide compositions and processes ofproducing same as disclosed herein can be apparent to one of skill inthe art viewing this disclosure.

In an aspect, a process of the present disclosure comprises reacting, ina reactor, a sulfur source (e.g., H₂S) and a feedstock comprising one ormore C₁₁₊ monoolefins in the presence of an initiating agent, aspreviously described herein for the branched C₁₀ monoolefins, to producea crude composition (also referred to as a crude product); wherein thecrude composition comprises mercaptans and C₂₂₊ sulfides.

In an aspect, a process of the present disclosure comprises reacting, ina reactor, a sulfur source (e.g., H₂S) and a feedstock comprising one ormore C₁₁₊ monoolefins in the presence of an initiating agent, aspreviously described herein for the branched C₁₀ monoolefins, to producea C₁₁₊ mercaptans crude composition; wherein the C₁₁₊ monoolefinscomprise C₁₁ and C₁₂ internal monoolefins, C₁₃ and C₁₄ internalmonoolefins, C₁₄ and C₁₆ linear alpha monoolefins, and the like, orcombinations thereof.

In an aspect, a process of the present disclosure comprises reacting, ina reactor, a sulfur source (e.g., H₂S) and a feedstock comprising one ormore C₁₁₊ monoolefins in the presence of an initiating agent, aspreviously described herein for the branched C₁₀ monoolefins, to producea C₁₁₊ mercaptans crude composition; wherein the one or more C₁₁₊monoolefins is selected from the group consisting of C₁₁ and C₁₂internal monoolefins, C₁₃ and C₁₄ internal monoolefins, C₁₄ and C₁₆linear alpha monoolefins, and combinations thereof.

In an aspect, a process of the present disclosure comprises reacting, ina reactor, a sulfur source (e.g., H₂S) and a feedstock comprising one ormore C₁₁₊ monoolefins in the presence of an initiating agent, aspreviously described herein for the branched C₁₀ monoolefins, to producea C₁₁₊ mercaptans crude composition; wherein the one or more C₁₁₊monoolefins is selected from the group consisting of C₁₁ and C₁₂internal monoolefins, C₁₃ and C₁₄ internal monoolefins, and C₁₄ and C₁₆linear alpha monoolefins.

The sulfur source can be any sulfur source suitable to provide sulfurfor the conversion of olefins (e.g., C₁₁₊ monoolefins) to mercaptans(e.g., C₁₁₊ mercaptans) and sulfides (e.g., C₂₂₊ sulfides). The sulfursource can comprise H₂S, thioacetic acid, and the like, or combinationsthereof. In some aspects, the sulfur source can comprise H₂S, aspreviously described herein.

In an aspect, the feedstock can comprise C₁₁ and C₁₂ internalmonoolefins. Any feedstock comprising C₁₁ and C₁₂ internal monoolefinsof the type described herein can be used, for example a feedstockobtained from a commercial petroleum refining or petrochemical process.Such feedstocks can comprise other olefins in addition to the C₁₁ andC₁₂ internal monoolefins of the type described herein, for example C¹⁰⁻monoolefins, as well as C₁₃₊ monoolefins. An example of a C₁₁ and C₁₂internal monoolefins feedstock suitable for use in the presentdisclosure include NEODENE 1112 IO higher olefins, which contains acombination of C₁₁ and C₁₂ internal olefins that is commerciallyavailable from Shell Chemicals. A typical composition of NEODENE 1112 IOhigher olefins is given in the table below:

Component of NEODENE 1112 IO Unit Value Method C₁₀ & % m/m <1.5 SMS*2976 Lower (C¹⁰⁻) [% mass/mass] C₁₁ % m/m 35-56 SMS 2976 C₁₂ % m/m 43-64SMS 2976 C₁₃ & % m/m <2.0 SMS 2976 Higher (C¹³⁻) Appearance Clear andsubstantially free of Visual visual impurities Color, Pt•Co <10 ASTMD1209 - 05(2011) Water mg/kg <100 ASTM E1064 - 16 *SMS = Shell ModifiedSpot Test.

In an aspect, the feedstock can comprise at least about 70 wt. %,alternatively at least about 75 wt. %, alternatively at least about 80wt. %, alternatively at least about 85 wt. %, alternatively at leastabout 90 wt. %, or alternatively at least about 95 wt. % C₁₁ and C₁₂internal monoolefins, based on the total weight of the feedstock. Insuch aspect, the feedstock can comprise (a) less than about 10 wt. %,alternatively less than about 5 wt. %, or alternatively less than about1.5 wt. % C¹⁰⁻ monoolefins; and (b) less than about 10 wt. %,alternatively less than about 5 wt. %, or alternatively less than about2 wt. % C₁₃₊ monoolefins; based on the total weight of the feedstock.For purposes of the disclosure herein, a feedstock comprising at leastabout 70 wt. % C₁₁ and C₁₂ internal monoolefins, based on the totalweight of the feedstock, can also be referred to as a “first C₁₁ and C₁₂feedstock.”

In another aspect, the feedstock can comprise at least about 95 wt. %,alternatively at least about 96 wt. %, alternatively at least about 97wt. %, alternatively at least about 98 wt. %, or alternatively at leastabout 99 wt. % C₁₁ and C₁₂ internal monoolefins, based on the totalweight of the feedstock. For purposes of the disclosure herein, afeedstock comprising at least about 95 wt. % C₁₁ and C₁₂ internalmonoolefins, based on the total weight of the feedstock, can also bereferred to as a “second C₁₁ and C₁₂ feedstock.” In an aspect, thesecond C₁₁ and C₁₂ feedstock can be produced by purifying the first C₁₁and C₁₂ feedstock, such as for example by distillation of the first C₁₁and C₁₂ feedstock.

In some aspects, the C₁₁ internal monoolefins and C₁₂ internalmonoolefins of any feedstock described herein (e.g., a first C₁₁ and C₁₂feedstock or a second C₁₁ and C₁₂ feedstock) can comprise linear C₁₁internal monoolefins and linear C₁₂ internal monoolefins, respectively.

In other aspects, the C₁₁ internal monoolefins and C₁₂ internalmonoolefins of any feedstock described herein (e.g., a first C₁₁ and C₁₂feedstock or a second C₁₁ and C₁₂ feedstock) can comprise branched C₁₁internal monoolefins and branched C₁₂ internal monoolefins,respectively. The branched C₁₁ internal monoolefins can comprise methylbranches. The branched C₁₂ internal monoolefins can comprise methylbranches.

In yet other aspects, the C₁₁ and C₁₂ internal monoolefins can compriselinear C₁₁ internal monoolefins, linear C₁₂ internal monoolefins,branched C₁₁ internal monoolefins, branched C₁₂ internal monoolefins, orcombinations thereof.

In some aspects, the feedstock can comprise (A) at least about 30 wt. %,alternatively at least about 35 wt. %, or alternatively at least about40 wt. % C₁₁ internal monoolefins, and (B) at least about 40 wt. %,alternatively at least about 45 wt. %, alternatively at least about 50wt. % C₁₂ internal monoolefins, based on the total weight of thefeedstock.

In an aspect, the feedstock can comprise C₁₃ and C₁₄ internalmonoolefins. Any feedstock comprising C₁₃ and C₁₄ internal monoolefinsof the type described herein can be used, for example a feedstockobtained from a commercial petroleum refining or petrochemical process.Such feedstocks can comprise other olefins in addition to the C₁₃ andC₁₄ internal monoolefins of the type described herein, for example C¹²⁻monoolefins, as well as C₁₅₊ monoolefins. An example of a C₁₃ and C₁₄internal monoolefins feedstock suitable for use in the presentdisclosure include NEODENE 1314 IO higher olefins (also known as NEODENE134 IO higher olefins), which contains a combination of C₁₃ and C₁₄internal olefins that is commercially available from Shell Chemicals. Atypical composition of NEODENE 1314 IO higher olefins is given in thetable below:

Component of NEODENE 1314 IO Unit Value Method C₁₂ & % m/m <2.0 SMS*2976 Lower (C¹²⁻) [% mass/mass] C₁₃ % m/m 43-55 SMS 2976 C₁₄ % m/m 45-55SMS 2976 C₁₅ & % m/m <2.5 SMS 2976 Higher (C¹⁵⁻) Appearance Clear andsubstantially free of Visual visual impurities Color, Pt•Co <10 ASTMD1209 - 05(2011) Water mg/kg <100 ASTM E1064 - 16 *SMS = Shell ModifiedSpot Test.

In an aspect, the feedstock can comprise at least about 70 wt. %,alternatively at least about 75 wt. %, alternatively at least about 80wt. %, alternatively at least about 85 wt. %, alternatively at leastabout 90 wt. %, or alternatively at least about 95 wt. % C₁₃ and C₁₄internal monoolefins, based on the total weight of the feedstock. Insuch aspect, the feedstock can comprise (a) less than about 10 wt. %,alternatively less than about 5 wt. %, or alternatively less than about2 wt. % C¹²⁻ monoolefins; and (b) less than about 10 wt. %,alternatively less than about 5 wt. %, or alternatively less than about2.5 wt. % C₁₅₊ monoolefins; based on the total weight of the feedstock.For purposes of the disclosure herein, a feedstock comprising at leastabout 70 wt. % C₁₃ and C₁₄ internal monoolefins, based on the totalweight of the feedstock, can also be referred to as a “first C₁₃ and C₁₄feedstock.”

In another aspect, the feedstock can comprise at least about 95 wt. %,alternatively at least about 96 wt. %, alternatively at least about 97wt. %, alternatively at least about 98 wt. %, or alternatively at leastabout 99 wt. % C₁₃ and C₁₄ internal monoolefins, based on the totalweight of the feedstock. For purposes of the disclosure herein, afeedstock comprising at least about 95 wt. % C₁₃ and C₁₄ internalmonoolefins, based on the total weight of the feedstock, can also bereferred to as a “second C₁₃ and C₁₄ feedstock.” In an aspect, thesecond C₁₃ and C₁₄ feedstock can be produced by purifying the first C₁₃and C₁₄ feedstock, such as for example by distillation of the first C₁₃and C₁₄ feedstock.

In some aspects, the C₁₃ internal monoolefins and C₁₄ internalmonoolefins of any feedstock described herein (e.g., a first C₁₃ and C₁₄feedstock or a second C₁₃ and C₁₄ feedstock) can comprise linear C₁₃internal monoolefins and linear C₁₄ internal monoolefins, respectively.

In other aspects, the C₁₃ internal monoolefins and C₁₄ internalmonoolefins of any feedstock described herein (e.g., a first C₁₃ and C₁₄feedstock or a second C₁₃ and C₁₄ feedstock) can comprise branched C₁₃internal monoolefins and branched C₁₄ internal monoolefins,respectively. The branched C₁₃ internal monoolefins can comprise methylbranches. The branched C₁₄ internal monoolefins can comprise methylbranches.

In yet other aspects, the C₁₃ and C₁₄ internal monoolefins can compriselinear C₁₃ internal monoolefins, linear C₁₄ internal monoolefins,branched C₁₃ internal monoolefins, branched C₁₄ internal monoolefins, orcombinations thereof.

In some aspects, the feedstock can comprise (A) at least about 35 wt. %,alternatively at least about 40 wt. %, or alternatively at least about45 wt. % C₁₃ internal monoolefins, and (B) at least about 35 wt. %,alternatively at least about 40 wt. %, alternatively at least about 45wt. % C₁₄ internal monoolefins; based on the total weight of thefeedstock.

In an aspect, the feedstock can comprise C₁₄ and C₁₆ alpha monoolefins,such as C₁₄ and C₁₆ linear alpha monoolefins. For purposes of thedisclosure herein, the terms “alpha olefin (monoolefin)” and “terminalolefin (monoolefin)” can be used interchangeably. Any feedstockcomprising C₁₄ and C₁₆ alpha monoolefins of the type described hereincan be used, for example a feedstock obtained from a commercialpetroleum refining or petrochemical process. Such feedstocks cancomprise other olefins in addition to the C₁₄ and C₁₆ alpha monoolefinsof the type described herein, for example C¹³⁻ monoolefins, as well asC₁₇₊ monoolefins. In some aspects, a feedstock comprising C₁₄ and C₁₆alpha monoolefins can further comprise C₁₅ monoolefins, such as C₁₅alpha monoolefin, C₁₅ linear alpha monoolefin, etc.

As will be appreciated by one of skill in the art, and with the help ofthis disclosure, a feedstock comprising linear olefins (e.g., linearalpha monoolefins, C₁₄ and C₁₆ linear alpha monoolefins) can furthercomprise a minor amount of branched monoolefins; or alternatively canexclude branched monoolefins. In some aspects, the feedstock comprisingC₁₄ and C₁₆ linear alpha monoolefins comprises less than 1 wt. %,alternatively less than 0.1 wt. %, alternatively less than 0.01 wt. %,alternatively less than 0.001 wt. %, or alternatively less than 0.0001wt. % branched monoolefins, based on the total weight of the feedstock.In an aspect, the feedstock comprising C₁₄ and C₁₆ linear alphamonoolefins is substantially free of branched monoolefins.

An example of a C₁₄ and C₁₆ alpha monoolefins feedstock suitable for usein the present disclosure include NEODENE 14/16 higher olefins, whichcontains a combination of C₁₄ and C₁₆ alpha olefins (2:1 blend of a highpurity 1-tetradecene (C₁₄) and 1-hexadecene (C₁₆) made by the ShellHigher Olefins Process (SHOP) by the oligomerization of ethylene) thatis commercially available from Shell Chemicals. A typical composition ofNEODENE 14/16 higher olefins is given in the table below:

Component of NEODENE 14/16 Unit Value Method C₁₂ and % m/m <2 SMS* 2895lower (C¹²⁻) [% mass/mass] C₁₄ % m/m 60-70 SMS 2895 C₁₆ % m/m 29-40 SMS2895 C₁₈ and % m/m <2 SMS 2895 higher (C₁₈₊) Total n-Alpha % m/m >92.5SMS 2895 Olefins Total Branched % m/m <4.5 SMS 2895 Olefins TotalInternal % m/m <2.5 SMS 2895 Olefins Paraffin % m/m <0.2 SMS 2895Appearance Clear and substantially free of Visual visual impuritiesColor, Pt•Co <5 ASTM D1209 - 05(2011) Water mg/kg <100 ASTM E1064 - 16Carbonyls as C═O mg/kg <15 SMS 2894 Peroxides as O mg/kg <3 SMS 359 *SMS= Shell Modified Spot Test.

In an aspect, the feedstock can comprise at least about 70 wt. %,alternatively at least about 75 wt. %, alternatively at least about 80wt. %, alternatively at least about 85 wt. %, alternatively at leastabout 90 wt. %, or alternatively at least about 95 wt. % C₁₄ and C₁₆linear alpha monoolefins, based on the total weight of the feedstock. Insuch aspect, the feedstock can comprise (a) less than about 10 wt. %,alternatively less than about 5 wt. %, or alternatively less than about2 wt. % C¹²⁻ monoolefins; and (b) less than about 10 wt. %,alternatively less than about 5 wt. %, or alternatively less than about2 wt. % C₁₈₊ monoolefins; based on the total weight of the feedstock.For purposes of the disclosure herein, a feedstock comprising at leastabout 70 wt. % C₁₄ and C₁₆ linear alpha monoolefins, based on the totalweight of the feedstock, can also be referred to as a “first C₁₄ and C₁₆feedstock.”

In another aspect, the feedstock can comprise at least about 95 wt. %,alternatively at least about 96 wt. %, alternatively at least about 97wt. %, alternatively at least about 98 wt. %, or alternatively at leastabout 99 wt. % C₁₄ and C₁₆ linear alpha monoolefins, based on the totalweight of the feedstock. For purposes of the disclosure herein, afeedstock comprising at least about 95 wt. % C₁₄ and C₁₆ linear alphamonoolefins, based on the total weight of the feedstock, can also bereferred to as a “second C₁₄ and C₁₆ feedstock.” In an aspect, thesecond C₁₄ and C₁₆ feedstock can be produced by purifying the first C₁₄and C₁₆ feedstock, such as for example by distillation of the first C₁₄and C₁₆ feedstock.

The feedstock comprising C₁₄ and C₁₆ linear alpha monoolefin (e.g., afirst C₁₄ and C₁₆ feedstock or a second C₁₄ and C₁₆ feedstock) cancomprise less than less than about 10 wt. %, alternatively less thanabout 7.5 wt. %, or alternatively less than about 4.5 wt. % branchedolefins, based on the total weight of the feedstock.

In some aspects, the feedstock can comprise (A) at least about 50 wt. %,alternatively at least about 55 wt. %, or alternatively at least about60 wt. % 1-tetradecene, and (B) at least about 20 wt. %, alternativelyat least about 25 wt. %, alternatively at least about 30 wt. %1-hexadecene, based on the total weight of the feedstock.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more C_(u+) monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins)can be reacted using a sulfur source to olefin molar ratio of from about1:1 to about 20:1, alternatively from about 2:1 to about 15:1, oralternatively from about 3:1 to about 10:1; as previously describedherein for the branched C₁₀ monoolefins.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins)can be reacted at a pressure of from about 30 psig (206 kPag) to about1,500 psig (10,300 kPag), alternatively from about 100 psig (690 kPag)to about 1,250 psig (8,600 kPag), or alternatively from about 250 psig(1,700 kPag) to about 1,000 psig (6,900 kPag); as previously describedherein for the branched C₁₀ monoolefins.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins)can be reacted (as previously described herein for the branched C₁₀monoolefins) to produce olefin conversion of equal to or greater thanabout 70%, alternatively equal to or greater than about 75%, oralternatively equal to or greater than about 80%, alternatively equal toor greater than about 85%, or alternatively equal to or greater thanabout 90%.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins)can be reacted in the presence of an initiating agent to produce amercaptans crude composition; wherein the initiating agent comprisesultraviolet (UV) radiation; as previously described herein for thebranched C₁₀ monoolefins. In such aspect, the initiating agent canfurther comprise a phosphite promoter, a photoinitiator, a sulfurscavenger, an antioxidant, and the like, or combinations thereof.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins)can be reacted in the presence of an initiating agent to produce a C₁₁₊mercaptans crude composition; wherein the initiating agent comprises aacid catalyst; as previously described herein for the branched C₁₀monoolefins.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins)can be reacted in the presence of an initiating agent to produce a C₁₁₊mercaptans crude composition; wherein the initiating agent comprises ahydrodesulfurization (HDS) catalyst; as previously described herein forthe branched C₁₀ monoolefins.

As noted previously, any suitable feedstocks comprising one or more C₁₁₊monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) can bereacted with a sulfur source (e.g., H₂S) in the presence of aninitiating agent to produce a C₁₁₊ mercaptans crude composition, and theC₁₁₊ mercaptans crude composition can be further refined (e.g.,distilled or otherwise separated into one or more fractions such aslights, intermediate, and heavies) to yield various compositionsdescribed herein. As described in more detail herein, the type and/oramounts of the constituent components that form the C₁₁₊ mercaptanscrude composition can vary depending upon the feedstock (e.g., theamount and types of olefins therein), the reaction conditions, thecatalysts employed, etc., and one skilled in the art can tailor the postreactor processing of the C₁₁₊ mercaptans crude composition to accountfor the specific compounds present in a given C₁₁₊ mercaptans crudecomposition to yield various desired products and compositions of thetypes described herein.

Upon completion of the reaction of a feedstock comprising one or moreC₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) with asulfur source (e.g., H₂S), a reactor effluent can be recovered from thereactor and H₂S removed therefrom to yield a C₁₁₊ mercaptans crudecomposition. The term “C₁₁₊ mercaptans crude composition” or “C₁₁₊mercaptans crude product” refers to an unrefined effluent streamrecovered from the reactor after removal of the sulfur source (e.g.,H₂S), and in particular to a sulfur source-free effluent stream that hasnot undergone any additional post-reactor processing such as flashing,distillation, or other separation techniques or processes to remove anycomponents from the effluent stream other than the initial removal ofthe sulfur source.

The C₁₁₊ mercaptans crude composition comprises C₁₁₊ mercaptans and C₂₂₊sulfides formed by the reaction of the sulfur source (e.g., H₂S) and theone or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins;C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alphamonoolefins), wherein the structures of these C₁₁₊ mercaptans and C₂₂₊sulfides are consistent with (e.g., derived from) the structures of thecorresponding C₁₁₊ monoolefins. For example, in aspects where the one ormore C₁₁₊ monoolefins comprise 1-tetradecene (H₂C═CH—(CH₂)₁₁—CH₃) and1-hexadecene (H₂C═CH—(CH₂)₁₃—CH₃), the resulting C₁₁₊ mercaptans (C₁₄mercaptans and C₁₆ mercaptans) can be characterized by the followingstructures that are consistent with (e.g., derived from) the structuresof the corresponding 1-tetradecene and 1-hexadecene:

and the resulting C₂₂₊ sulfides (C₂₈ sulfides, C₃₀ sulfides, and C₃₂sulfides) can be characterized by the following structures that areconsistent with (e.g., derived from) the structures of the corresponding1-tetradecene and 1-hexadecene:H₃C—(CH₂)₁₃—S—(CH₂)₁₃—CH₃ (C₂₈ sulfide);H₃C—(CH₂)₁₁—CH(CH₃)—S—CH(CH₃)—(CH₂)₁₁—CH₃ (C₂₈ sulfide);H₃C—(CH₂)₁₁—CH(CH₃)—S—(CH₂)₁₁—CH₃ (C₂₈ sulfide);H₃C—(CH₂)₁₃—S—(CH₂)₁₅—CH₃ (C₃₀ sulfide);H₃C—(CH₂)₁₁—CH(CH₃)—S—CH(CH₃)—(CH₂)₁₃—CH₃ (C₃₀ sulfide);H₃C—(CH₂)₁₃—CH(CH₃)—S—(CH₂)₁₃—CH₃ (C₃₀ sulfide);H₃C—(CH₂)₁₁—CH(CH₃)—S—(CH₂)₁₅—CH₃ (C₃₀ sulfide);H₃C—(CH₂)₁₅—S—(CH₂)₁₅—CH₃ (C₃₂ sulfide);H₃C—(CH₂)₁₃—CH(CH₃)—S—CH(CH₃)—(CH₂)₁₃—CH₃ (C₃₂ sulfide);H₃C—(CH₂)₁₃—CH(CH₃)—S—(CH₂)₁₅—CH₃ (C₃₂ sulfide); etc.

Generally, the C₁₁₊ mercaptans are characterized by structure R⁶—SH,wherein R⁶ is a functional group (e.g., alkyl group) derived from theone or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins;C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alphamonoolefins) disclosed herein.

Generally, the C₂₂₊ sulfides are characterized by structure R⁷—S—R⁸,wherein both R⁷ and R⁸ can each independently be a functional groupderived from the one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂internal monoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆linear alpha monoolefins) disclosed herein. R⁷ and R⁸ can be the same ordifferent, e.g., R⁷ and R⁸ can have the same structure; R⁷ and R⁸ canhave different structures; R⁷ and R⁸ can have the same chain length; R⁷and R⁸ can have different chain length; etc.

As will be appreciated by one of skill in the art, and with the help ofthis disclosure, in aspects where the one or more C₁₁₊ monoolefins(e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄ internalmonoolefins) contain methyl branches in their structure, the resultingC₁₁₊ mercaptans and C₂₂₊ sulfides would also contain methyl branchesconsistent with (e.g., derived from) the structures of the correspondingC₁₁₊ monoolefins.

In addition to C₁₁₊ mercaptans and C₂₂₊ sulfides, the C₁₁₊ mercaptanscrude composition can comprise a number of other compounds such asunreacted olefins, inert compounds (e.g., alkanes), C¹⁰⁻ mercaptans,C²¹⁻ sulfides, and other impurities. The constituent componentscontained within the C₁₁₊ mercaptans crude composition can varydepending upon the composition of the feedstock (e.g., an unpurifiedfeedstock as compared to a purified feedstock as described herein) aswell as reaction conditions, catalyst, etc. In various aspects, a C₁₁₊mercaptans crude composition can comprise light, intermediate, and heavyfractions as described herein.

In some aspects, the C₁₁₊ mercaptans crude composition can comprise lessthan about 10 wt. %, alternatively less than about 5 wt. %,alternatively less than about 4 wt. %, alternatively at less than about3 wt. %, alternatively less than about 2 wt. %, or alternatively lessthan about 1 wt. % C₂₂₊ sulfides, based on the total weight of the crudecomposition, wherein the C₂₂₊ sulfides are characterized by structureR⁷—S—R⁸, wherein both R⁷ and R⁸ can each independently be a functionalgroup derived from the one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂internal monoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆linear alpha monoolefins) disclosed herein.

In an aspect, a process of the present disclosure can further compriserecovering a reaction product from the C₁₁₊ mercaptans crudecomposition; wherein the reaction product can comprises mercaptansand/or C₂₂₊ sulfides, wherein the C₁₁₊ mercaptans are characterized bystructure R⁶—SH, wherein R⁶ is a functional group (e.g., alkyl group)derived from the one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂internal monoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆linear alpha monoolefins) disclosed herein; and wherein the C₂₂₊sulfides are characterized by structure R⁷—S—R⁸, wherein both R⁷ and R⁸can each independently be a functional group derived from the one ormore C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ andC₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins)disclosed herein.

In an aspect, the reaction product can comprise a C₁₁₊ mercaptanscomposition (intermediate fraction), a C₂₂₊ sulfides composition (heavyfraction), a C₁₁₊ mercaptans/C₂₂₊ sulfides composition (intermediate andheavy fractions), or combinations thereof.

In an aspect, a C₁₁₊ mercaptans crude composition as disclosed hereincan be separated into two or more fractions (e.g., light fraction,intermediate fraction, heavy fraction, etc.) by any process or unitoperation known in the art. For example, a C₁₁₊ mercaptans crudecomposition can be processed (e.g., distilled) to remove a fraction oflight compounds. Alternatively, a C₁₁₊ mercaptans crude composition canbe processed to recover both a light fraction and an intermediatefraction (e.g., a rough cut), followed by further processing to obtainone or more fine cuts. Alternatively, a C₁₁₊ mercaptans crudecomposition can be processed to recover a heavy fraction (e.g., a C₂₂₊sulfide fraction). Alternatively, a C₁₁₊ mercaptans crude compositioncan be processed to separate out any combination of a light fraction, anintermediate fraction (e.g., comprising C₁₁₊ mercaptans), and a heavyfraction (e.g., comprising C₂₂₊ sulfides). Furthermore, a light,intermediate or heavy fraction (e.g., a rough cut) can be furtherprocessed or parsed to obtain one or more desired fine cuts (e.g., aC₁₁₊ mercaptan fraction). Alternatively, a C₁₁₊ mercaptans crudecomposition can be separated to produce a high-purity C₁₁₊ mercaptanstream and/or a high-purity C₂₂₊ sulfide stream (e.g., to obtain adesired fine cut or fraction such as a C₁₁₊ mercaptan fraction).Further, these separated streams can be blended in any combination ofratios to produce a mixture with specific concentrations of one of morecomponents (e.g., desired blend ratios of C₁₁₊ mercaptans and/or C₂₂₊sulfides, for example to aid in a particular end use). The unitoperations/processes used for these separations are known to one ofskill and the art and include, but are not limited to, distillation,fractionation, flashing, stripping, and absorption, and others. The unitoperation conditions, such as for example, temperature, pressure, flowrates, and others at which these unit operations produce one or more ofthe desired fractions can easily be determined by one of ordinary skillin the art.

In an aspect, a light fraction is removed from the C₁₁₊ mercaptans crudecomposition, for example by flashing, distillation, fractionation,stripping, absorption, etc.

In an aspect, the light fraction removed from the C₁₁₊ mercaptans crudecomposition can comprise at least about 90 wt. %, alternatively at leastabout 90 wt. %, alternatively at least about 95 wt. %, alternatively atleast about 96 wt. %, alternatively at least about 97 wt. %,alternatively at least about 98 wt. %, alternatively at least about 99wt. % C¹⁰⁻ compounds, based on the total weight of the light fraction.Nonlimiting examples of C¹⁰⁻ compounds include C¹⁰⁻ monoolefins (e.g.,unreacted C¹⁰⁻ monoolefins), C¹⁰⁻ mercaptans, C¹⁰⁻ alkanes, C¹⁰⁻alcohols, and the like, or combinations thereof. In an aspect, the lightfraction removed from the C₁₁₊ mercaptans crude composition can compriseless than about 10 wt. %, alternatively less than about 5 wt. %,alternatively less than about 4 wt. %, alternatively at less than about3 wt. %, alternatively less than about 2 wt. %, or alternatively lessthan about 1 wt. % C₁₁₊ compounds, based on the total weight of thelight fraction.

Following removal of the lights (for example, via flashing) from themercaptans crude composition, a combined intermediate and heavy fraction(i.e., C₁₁₊ compounds sometimes referred to as a kettle product in theExamples) can remain, and the combined intermediate and heavy fractioncan be used “as is” or can be further processed, for example separatedor split into separate intermediate and heavy fractions (and saidseparate intermediate and heavy fractions can be subsequently recombinedin various blends and associated blend ratios), as described in moredetail herein. In an aspect, a combined intermediate and heavy fraction(i.e., C₁₁₊ compounds) formed by removal of the light fraction from themercaptans crude composition can comprise less than about 15 wt. %,alternatively less than about 10 wt. %, alternatively less than about 9wt. %, alternatively less than about 8 wt. %, alternatively less thanabout 7 wt. %, alternatively less than about 6 wt. %, alternatively lessthan about 5 wt. %, alternatively less than about 4 wt. %, alternativelyless than about 3 wt. %, alternatively less than about 2 wt. %,alternatively less than about 1 wt. % C¹⁰⁻ products, based on the totalweight of the combined intermediate and heavy fraction (i.e., C₁₁₊compounds).

In an aspect, a combined intermediate and heavy fraction (i.e., C₁₁₊compounds) recovered from the from the C₁₁₊ mercaptans crude compositioncan comprise (A) at least about 50 wt. %, alternatively at least about60 wt. %, alternatively at least about 70 wt. %, alternatively at leastabout 80 wt. %, alternatively at least about 90 wt. %, alternatively atleast about 95 wt. %, or alternatively at least about 99 wt. % C₁₁₊mercaptans, based on the total weight of the combined fraction, whereinthe C₁₁₊ mercaptans are characterized by structure R⁶—SH, wherein R⁶ isa functional group (e.g., alkyl group) derived from the one or more C₁₁₊monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) disclosedherein; and (B) less than about 20 wt. %, alternatively less than about15 wt. %, alternatively less than about 10 wt. %, or alternatively lessthan about 5 wt. % C₂₂₊ sulfides, based on the total weight of thecombined fraction, wherein the C₂₂₊ sulfides are characterized bystructure R⁷—S—R⁸, wherein both R⁷ and R⁸ can each independently be afunctional group derived from the one or more C₁₁₊ monoolefins (e.g.,C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄ internal monoolefins; orC₁₄ and C₁₆ linear alpha monoolefins) disclosed herein.

In an embodiment, the C₁₁₊ mercaptans crude composition can be flashedto remove a lights fraction as described herein to produce a combinedintermediate and heavy fraction (i.e., C₁₁₊ compounds) comprising: (A)from at least about 50 wt. % to at least about 99 wt. %, alternativelyfrom at least about 50 wt. % to at least about 95 wt. %, alternativelyfrom at least about 55 wt. % to at least about 85 wt. %, oralternatively from at least about 60 wt. % to at least about 80 wt. %C₁₁₊ mercaptans, wherein at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 75 wt. %, alternatively at least about 80 wt. %, oralternatively at least about 85 wt. % of the C₁₁₊ mercaptans can be C₁₁₊mercaptans characterized by structure R⁶—SH, wherein R⁶ is a functionalgroup (e.g., alkyl group) derived from the one or more C₁₁₊ monoolefins(e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄ internalmonoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) disclosed herein;and (B) from about 1 wt. % to about 20 wt. %, alternatively from about 5wt. % to about 20 wt. %, alternatively from about 7.5 wt. % to about17.5 wt. %, or alternatively from about 10 wt. % to about 15 wt. % C₂₂₊sulfides; wherein at least about 50 wt. %, alternatively at least about60 wt. %, alternatively at least about 70 wt. %, alternatively at leastabout 75 wt. %, alternatively at least about 80 wt. %, or alternativelyat least about 85 wt. % of the C₂₂₊ sulfides can be C₂₂₊ sulfidescharacterized by structure R⁷—S—R⁸, wherein both R⁷ and R⁸ can eachindependently be a functional group derived from the one or more C₁₁₊monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) disclosedherein.

In an aspect, the C₁₁₊ mercaptans crude composition can be flashed toremove a light fraction and subsequently further separated to produce anintermediate fraction and a heavy fraction (i.e., C₁₁₊ compounds). Theintermediate fraction and the heavy fractions recovered from the C₁₁₊mercaptans crude composition can then be optionally further processed(e.g., polished) and mixed in any appropriate ratio to produce blendedcompositions, as previously described herein for crude compositionsderived from branched C₁₀ monoolefins.

In an aspect, an intermediate fraction recovered from the C₁₁₊mercaptans crude composition can comprise at least about 25 wt. %,alternatively at least about 30 wt. %, alternatively at least about 40wt. %, alternatively at least about 50 wt. %, alternatively at leastabout 75 wt. %, or alternatively at least about 85 wt. % C₁₁₊mercaptans, based on the total weight of the intermediate fraction,wherein the C₁₁₊ mercaptans are characterized by structure R⁶—SH,wherein R⁶ is a functional group (e.g., alkyl group) derived from theone or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins;C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alphamonoolefins) disclosed herein.

In an aspect, the heavy fraction recovered from the mercaptans crudecomposition can comprise at least about 5, 10, 15, 20, 25, 30, 35, 40,45, 50, 55, 60, 65, 70, 75, 80, or 85 wt. %, C₂₂₊ sulfides, based on thetotal weight of the heavy fraction, wherein the C₂₂₊ sulfides arecharacterized by structure R⁷—S—R⁸, wherein both R⁷ and R⁸ can eachindependently be a functional group derived from the one or more C₁₁₊monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) disclosedherein.

In an aspect, a C₁₁₊ mercaptans composition can comprise C₁₁₊mercaptans, wherein at least a portion of the C₁₁₊ mercaptans arecharacterized by structure R⁶—SH, wherein R⁶ is a functional group(e.g., alkyl group) derived from the one or more C₁₁₊ monoolefins (e.g.,C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄ internal monoolefins; orC₁₄ and C₁₆ linear alpha monoolefins) disclosed herein. In an aspect,the C₁₁₊ mercaptans composition can comprise any suitable amount of C₁₁₊mercaptans as disclosed herein.

In some aspects, a C₁₁₊ mercaptans composition can comprise at leastabout 50 wt. %, alternatively at least about 60 wt. %, alternatively atleast about 70 wt. %, alternatively at least about 80 wt. %,alternatively at least about 90 wt. %, alternatively at least about 95wt. %, or alternatively at least about 99 wt. % C₁₁₊ mercaptans, basedon the total weight of the C₁₁₊ mercaptans composition; wherein at leastabout 50 wt. %, alternatively at least about 60 wt. %, alternatively atleast about 70 wt. %, alternatively at least about 75 wt. %,alternatively at least about 80 wt. %, or alternatively at least 85 wt.% of the C₁₁₊ mercaptans can be C₁₁₊ mercaptans characterized bystructure R⁶—SH, wherein R⁶ is a functional group (e.g., alkyl group)derived from the one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂internal monoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆linear alpha monoolefins) disclosed herein.

In other aspects, a C₁₁₊ mercaptans composition can consist of orconsist essentially of C₁₁₊ mercaptans characterized by structure R⁶—SH,wherein R⁶ is a functional group (e.g., alkyl group) derived from theone or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins;C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linear alphamonoolefins) disclosed herein.

In yet other aspects, a C₁₁₊ mercaptans composition can comprise atleast about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,75, 80, 85, 90, 95, or 99 wt. % C₁₁₊ mercaptans characterized bystructure R⁶—SH, wherein R⁶ is a functional group (e.g., alkyl group)derived from the one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂internal monoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆linear alpha monoolefins) disclosed herein.

In an aspect, a C₂₂₊ sulfides composition can comprise C₂₂₊ sulfides,wherein at least a portion of the C₂₂₊ sulfides are characterized bystructure R⁷—S—R⁸, wherein both R⁷ and R⁸ can each independently be afunctional group derived from the one or more C₁₁₊ monoolefins (e.g.,C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄ internal monoolefins; orC₁₄ and C₁₆ linear alpha monoolefins) disclosed herein. In an aspect,the C₂₂₊ sulfides composition can comprise any suitable amount of C₂₂₊sulfides as disclosed herein.

In some aspects, a C₂₂₊ sulfides composition can comprise C₂₂₊ sulfides,wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 80wt. %, alternatively at least about 90 wt. %, alternatively at leastabout 95 wt. %, or alternatively at least about 99 wt. % of the C₂₂₊sulfides can be C₂₂₊ sulfides characterized by structure R⁷—S—R⁸,wherein both R⁷ and R⁸ can each independently be a functional groupderived from the one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂internal monoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆linear alpha monoolefins) disclosed herein.

In other aspects, a C₂₂₊ sulfides composition can consist of or consistessentially of C₂₂₊ sulfides characterized by structure R⁷—S—R⁸, whereinboth R⁷ and R⁸ can each independently be a functional group derived fromthe one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internalmonoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linearalpha monoolefins) disclosed herein.

In yet other aspects, a C₂₂₊ sulfides composition comprises at leastabout 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,85, 90, 95, or 99 wt. % C₂₂₊ sulfides characterized by structureR⁷—S—R⁸, wherein both R⁷ and R⁸ can each independently be a functionalgroup derived from the one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂internal monoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆linear alpha monoolefins) disclosed herein.

In an aspect, a C₁₁₊ mercaptans/C₂₂₊ sulfides composition can compriseone or more C₁₁₊ mercaptans and one or more C₂₂₊ sulfides of the typedisclosed herein. In an aspect, the C₁₁₊ mercaptans/C₂₂₊ sulfidescomposition can comprise any suitable amount of C₁₁₊ mercaptans, and anysuitable amount of C₂₂₊ sulfides.

In an aspect, a C₁₁₊ mercaptans/C₂₂₊ sulfides composition can comprise(A) at least about 1 wt. %, alternatively at least about 5 wt. %,alternatively at least about 10 wt. %, alternatively at least about 15wt. %, alternatively at least about 20 wt. %, alternatively at leastabout 25 wt. %, alternatively at least about 30 wt. %, alternatively atleast about 40 wt. %, alternatively at least about 50 wt. %,alternatively at least about 60 wt. %, alternatively at least about 70wt. %, alternatively at least about 80 wt. %, alternatively at leastabout 90 wt. %, alternatively at least about 95 wt. %, or alternativelyat least about 99 wt. % C₁₁₊ mercaptans, based on the total weight ofthe mercaptans/C₂₂₊ sulfides composition, wherein at least a portion ofthe C₁₁₊ mercaptans can be C₁₁₊ mercaptans characterized by structureR⁶—SH, wherein R⁶ is a functional group (e.g., alkyl group) derived fromthe one or more C₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internalmonoolefins; C₁₃ and C₁₄ internal monoolefins; or C₁₄ and C₁₆ linearalpha monoolefins) disclosed herein; and (B) at least about 1 wt. %,alternatively at least about 5 wt. %, alternatively at least about 10wt. %, alternatively at least about 15 wt. %, alternatively at leastabout 20 wt. %, alternatively at least about 25 wt. %, alternatively atleast about 30 wt. %, alternatively at least about 40 wt. %,alternatively at least about 50 wt. %, alternatively at least about 60wt. %, alternatively at least about 70 wt. %, alternatively at leastabout 80 wt. %, alternatively at least about 90 wt. %, alternatively atleast about 95 wt. %, or alternatively at least about 99 wt. % C₂₂₊sulfides, based on the total weight of the C₁₁₊ mercaptans/C₂₂₊ sulfidescomposition, wherein at least a portion of the C₂₂₊ sulfides can be C₂₂₊sulfides characterized by structure R⁷—S—R⁸, wherein both R⁷ and R⁸ caneach independently be a functional group derived from the one or moreC₁₁₊ monoolefins (e.g., C₁₁ and C₁₂ internal monoolefins; C₁₃ and C₁₄internal monoolefins; or C₁₄ and C₁₆ linear alpha monoolefins) disclosedherein.

In an aspect, a C₁₁₊ mercaptans/C₂₂₊ sulfides composition can compriseC₁₁₊ mercaptans represented by structure R⁶—SH and/or C₂₂₊ sulfidesrepresented by structure R⁷—S—R⁸ that are formed by reacting an olefinfeedstock comprising C₁₁₊ monoolefins with H₂S as disclosed herein,wherein the C₁₁₊ monoolefins present in the olefin feedstock provide thealkyl group represented by R⁶, R⁷, and R⁸. In such aspects, the R⁶ groupof the C₁₁₊ mercaptans and/or the R⁷ and R⁸ groups of the C₂₂₊ sulfidesare provided by or derived from the counterpart R⁶, R⁷, and R⁸ groupspresent in the C₁₁₊ monoolefins in the olefin feedstock.

The C₁₁₊ mercaptans compositions, C₂₂₊ sulfides compositions, and C₁₁₊mercaptans/C₂₂₊ sulfides compositions can be salable or otherwise usedfor a variety of end uses such as mining ore collector compositions andchain transfer agents.

In an aspect, the C₁₁₊ mercaptans as disclosed herein can be furtherconverted to multi-sulfur containing compounds, which could then be usedfor any suitable applications, such as adhesives, epoxy adhesives, chaintransfer agents, catalyst sulfurization, lubricants, mining collectors,etc. In some aspects, the C₁₁₊ mercaptans as disclosed herein can befurther converted to polysulfides, which could then be used for epoxyadhesives. In other aspects, the mercaptans as disclosed herein can befurther converted to trithiocarbonates, which could then be used aschain transfer agents.

In an aspect, a C₁₁₊ mercaptans composition and/or a C₁₁₊mercaptans/C₂₂₊ sulfides composition comprising equal to or greater thanabout 25 wt. % C₁₁₊ mercaptans as disclosed herein can advantageouslyhave an odor less unpleasant than an odor of an otherwise similarcomposition comprising equal to or greater than about 25 wt. % n-dodecylmercaptan and/or tert-dodecyl mercaptan, as perceived by equal to orgreater than about 51% of human subjects exposed to the odor of eachcomposition. Additional advantages of the C₁₁₊ mercaptans compositions,C₂₂₊ sulfides compositions, and C₁₁₊ mercaptans/C₂₂₊ sulfidescompositions and processes of producing same as disclosed herein can beapparent to one of skill in the art viewing this disclosure.

In an aspect, a process of the present disclosure comprises reacting, ina reactor, a sulfur source (e.g., H₂S) and a feedstock comprising one ormore branched C₁₀₊ monoolefins in the presence of an initiating agent,as previously described herein for the branched C₁₀ monoolefins, toproduce a crude composition (also referred to as a crude product);wherein the crude composition comprises branched C₁₀₊ mercaptans andbranched C₂₀₊ sulfides.

In an aspect, a process of the present disclosure comprises reacting, ina reactor, a sulfur source (e.g., H₂S) and a feedstock comprising one ormore branched C₁₀₊ monoolefins in the presence of an initiating agent,as previously described herein for the branched C₁₀ monoolefins, toproduce a branched C₁₀₊ mercaptans crude composition (also referred toas a branched C₁₀₊ mercaptans crude product); wherein the branched C₁₀₊monoolefins comprise C₁₀ to C₃₀ monoolefins, alternatively C₁₁ to C₃₀monoolefins, alternatively C₁₂ to C₃₀ monoolefins, alternatively C₁₄ toC₃₀ monoolefins, alternatively C₁₆ to C₂₈ monoolefins, or alternativelyC₁₈ to C₂₆ monoolefins; and wherein the branched C₁₀₊ mercaptans crudecomposition comprises branched C₁₀₊ mercaptans and branched C₂₀₊sulfides.

The sulfur source can be any sulfur source suitable to provide sulfurfor the conversion of olefins (e.g., branched C₁₀₊ monoolefins) tomercaptans (e.g., branched C₁₀₊ mercaptans) and sulfides (e.g., branchedC₂₀₊ sulfides). The sulfur source can comprise H₂S, thioacetic acid, andthe like, or combinations thereof. In some aspects, the sulfur sourcecan comprise H₂S, as previously described herein.

The branched C₁₀₊ mercaptans crude composition can be further processed,for example via distillation, as previously described herein for thebranched C₁₀ monoolefins, to yield one or more products (also referredto as distilled, purified, refined, finished, or final products)selected from the group consisting of mercaptan compositions (e.g., acomposition comprising one or more branched C_(m+) mercaptans), sulfidecompositions (e.g., a composition comprising one or more branched C₂₀₊sulfides); and compositions having both mercaptans (e.g., branched C₁₀₊mercaptans) and sulfides (e.g., branched C₂₀₊ sulfides), referred to asmercaptan/sulfide compositions.

In an aspect, a C₁₀₊ mercaptans composition comprises one or morebranched C₁₀₊ mercaptans, wherein the branched C₁₀₊ mercaptans compriseC₁₀ to C₃₀ mercaptans, alternatively C₁₁ to C₃₀ mercaptans,alternatively C₁₂ to C₃₀ mercaptans, alternatively C₁₄ to C₃₀mercaptans, alternatively C₁₆ to C₂₈ mercaptans, or alternatively C₁₈ toC₂₆ mercaptans.

In an aspect, a C₂₀₊ sulfides composition comprises one or more branchedC₂₀₊ sulfides represented by the structure R¹⁰—S—R¹¹, wherein R¹⁰ andR¹¹ are each independently a functional group derived from an olefin,wherein the olefin comprises a branched C₁₀₊ monoolefin as disclosedherein. The branched C₂₀₊ sulfides comprise C₂₀ to C₆₀ sulfides,alternatively C₂₁ to C₆₀ sulfides, alternatively C₂₂ to C₆₀ sulfides,alternatively C₂₄ to C₆₀ sulfides, alternatively C₂₈ to C₆₀ sulfides,alternatively C₃₂ to C₅₆ sulfides, or alternatively C₃₆ to C₅₂ sulfides.

In an aspect, a C₁₀₊ mercaptans/C₂₀₊ sulfides composition comprises (A)one or more branched C₁₀₊ mercaptans; and (B) one or more branched C₂₀₊sulfides represented by the structure R¹⁰—S—R¹¹.

The C₁₀₊ mercaptans compositions, C₂₀₊ sulfides compositions, and C₁₀₊mercaptans/C₂₀₊ sulfides compositions can be salable or otherwise usedfor a variety of end uses such as mining ore collector compositions andchain transfer agents.

In an aspect, the compositions disclosed herein can be prepared by aprocess comprising reacting, in a reactor, a sulfur source (e.g., H₂S)and a feedstock comprising one or more branched C₁₀₊ monoolefins in thepresence of an initiating agent to produce a branched C₁₀₊ mercaptanscrude (reaction product) composition, wherein the branched C₁₀₊monoolefins comprise a branched C₁₀₊ monoolefin represented by StructureI-1, a branched C₁₀₊ monoolefin represented by Structure J-1, a branchedC₁₀₊ monoolefin represented by Structure K-1, a branched C₁₀₊ monoolefinrepresented by Structure L-1, or combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group. The R⁹ can be a linear C₁ to C₂₁ alkyl group or abranched C₁ to C₂₁ alkyl group. As will be appreciated by one of skillin the art, and with the help of this disclosure, the C₁₀₊ monoolefinscomprising the R⁹ alkyl group are branched monoolefins, regardless ofwhether R⁹ is linear or branched, owing to a branched sub-structure thatis linked to the R⁹ alkyl group, as it can be seen in Structures I-1,J-1, K-1, and L-1.

In some aspects, R⁹ can be selected from the group consisting of amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, adecyl group, an undecyl group, a dodecyl group, a tridecyl group, atetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecylgroup, an octadecyl group, a nonadecyl group, an eicosyl group, ahenicosyl group, and combinations thereof.

In aspects where R⁹ is a methyl group, the branched C₁₀₊ monoolefinscomprise one or more branched C₁₀ monoolefins, as previously disclosedherein. The branched C₁₀ monoolefins can comprise 5-methyl-1-nonene(represented by Structure I), 3-propyl-1-heptene (represented byStructure J), 4-ethyl-1-octene (represented by Structure K),2-butyl-1-hexene (represented by Structure L), or combinations thereof.

Any feedstock comprising one or more branched C₁₀₊ monoolefins of thetype described herein can be used, for example a feedstock obtained froma commercial petroleum refining or petrochemical process. Suchfeedstocks can comprise other olefins in addition to the one or morebranched C₁₀₊ monoolefins of the type described herein, for examplelinear C₁₀₊ monoolefins as well as olefins having less than 10 carbonatoms.

In an aspect, the feedstock can comprise one or more branched C₁₀ to C₃₀monoolefins. Any feedstock comprising branched C₁₀ to C₃₀ monoolefins ofthe type described herein can be used, for example a feedstock obtainedfrom a commercial petroleum refining or petrochemical process. Suchfeedstocks can comprise other olefins in addition to the branched C₁₀ toC₃₀ monoolefins of the type described herein, for example C⁹⁻monoolefins, C₃₁₊ monoolefins, as well as linear C₁₀ to C₃₀ monoolefins.

In an aspect, the feedstock can comprise at least about 70 wt. %,alternatively at least about 75 wt. %, alternatively at least about 80wt. %, alternatively at least about 85 wt. %, alternatively at leastabout 90 wt. %, or alternatively at least about 95 wt. % branched C₁₀ toC₃₀ monoolefins, based on the total weight of the feedstock. In suchaspect, the feedstock can comprise (a) less than about 15 wt. %,alternatively less than about 10 wt. %, alternatively less than about 5wt. %, or alternatively less than about 1 wt. % C⁹⁻ monoolefins; and (b)less than about 15 wt. %, alternatively less than about 10 wt. %,alternatively less than about 5 wt. %, or alternatively less than about1 wt. % C₃₁₊ monoolefins; based on the total weight of the feedstock.For purposes of the disclosure herein, a feedstock comprising at leastabout 70 wt. % branched C₁₀ to C₃₀ monoolefins, based on the totalweight of the feedstock, can also be referred to as a “first C₁₀ to C₃₀feedstock.”

In another aspect, the feedstock can comprise at least about 95 wt. %,alternatively at least about 96 wt. %, alternatively at least about 97wt. %, alternatively at least about 98 wt. %, or alternatively at leastabout 99 wt. % branched C₁₀ to C₃₀ monoolefins, based on the totalweight of the feedstock. For purposes of the disclosure herein, afeedstock comprising at least about 95 wt. % branched C₁₀ to C₃₀monoolefins, based on the total weight of the feedstock, can also bereferred to as a “second C₁₀ to C₃₀ feedstock.” In an aspect, the secondC₁₀ to C₃₀ feedstock can be produced by purifying the first C₁₀ to C₃₀feedstock, such as for example by distillation of the first C₁₀ to C₃₀feedstock.

In an aspect, the C₁₀ to C₃₀ monoolefins of any feedstock describedherein (e.g., a first C₁₀ to C₃₀ feedstock or a second C₁₀ to C₃₀feedstock) can comprise, can consist essentially of, or can be, abranched C₁₀₊ monoolefin represented by Structure I-1, a branched C₁₀₊monoolefin represented by Structure J-1, a branched C₁₀₊ monoolefinrepresented by Structure K-1, and a branched C₁₀₊ monoolefin representedby Structure L-1; wherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively aC₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁ alkyl group,alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉ alkylgroup, or alternatively a C₉ to C₁₇ alkyl group.

In an aspect, the C₁₀ to C₃₀ monoolefins of any feedstock describedherein (e.g., a first C₁₀ to C₃₀ feedstock or a second C₁₀ to C₃₀feedstock) can comprise linear C₁₀ to C₃₀ monoolefins. In an aspect, theC₁₀ to C₃₀ monoolefins of any feedstock described herein can compriseless than or equal to about 26 mol %, alternatively less than or equalto about 24 mol %, alternatively less than or equal to about 22 mol %,alternatively less than or equal to about 20 mol %, or alternativelyless than or equal to about 18 mol % linear C₁₀ to C₃₀ monoolefins. Insome aspects, the C₁₀ to C₃₀ monoolefins of any feedstock describedherein can comprise from about 0.1 mol % to about 26 mol %,alternatively from about 0.5 mol % to about 24 mol %, alternatively fromabout 1 mol % to about 22 mol %, alternatively from about 1.5 mol % toabout 20 mol %, or alternatively from about 2.5 mol % to about 18 mol %linear C₁₀ to C₃₀ monoolefins.

In an aspect, the first C₁₀ to C₃₀ feedstock disclosed herein canfurther comprise C⁹⁻ monoolefins, C₃₁₊ monoolefins, or combinationsthereof; alternatively, C⁹⁻ monoolefins; or alternatively, C₃₁₊monoolefins. In an aspect, the C⁹⁻ monoolefins can comprise, can consistessentially of, or can be, a C₇ monoolefin, a C₈ monoolefin, a C₉monoolefin, or combinations thereof; alternatively, a C₇ monoolefin;alternatively, a C₈ monoolefin; or alternatively, a C₉ monoolefin. Insome aspects, the C⁹⁻ monoolefins can comprise, can consist essentiallyof, or can be, a C₈ monoolefin. In an aspect, the C₃₁₊ monoolefins cancomprise, can consist essentially of, or can be, a C₃₁ monoolefin, a C₃₂monoolefin, a C₃₃ monoolefin, a C₃₄ monoolefin, a C₃₅ monoolefin, a C₃₆monoolefin, a C₃₇ monoolefin, a C₃₈ monoolefin, or combinations thereof;alternatively, a C₃₁ monoolefin; alternatively, a C₃₂ monoolefin;alternatively, a C₃₃ monoolefin; alternatively, a C₃₄ monoolefin;alternatively, a C₃₅ monoolefin; alternatively, a C₃₆ monoolefin;alternatively, a C₃₇ monoolefin; or alternatively, a C₃₈ monoolefin. Insome aspects, the C₃₁₊ monoolefins can comprise, can consist essentiallyof, or can be, a C₃₂ monoolefin, a C₃₆ monoolefin, a C₃₈ monoolefin, orcombinations thereof; alternatively, a C₃₂ monoolefin; alternatively, aC₃₆ monoolefin; or alternatively, a C₃₈ monoolefin.

In an aspect, the first C₁₀ to C₃₀ feedstock can further comprise fromabout 0.1 mol % to about 5 mol %, alternatively from about 0.25 mol % toabout 4 mol %, or alternatively from about 0.5 mol % to about 3 mol % C₈monoolefins. In such aspect, the C₈ monoolefins can comprise at leastabout 95 mol %, alternatively at least about 96 mol %, alternatively atleast about 97 mol %, alternatively at least about 98 mol %, oralternatively at least about 99 mol % 1-octene.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more branched C₁₀ to C₃₀ monoolefins can be reacted using a sulfursource to olefin molar ratio of from about 1:1 to about 20:1,alternatively from about 2:1 to about 15:1, or alternatively from about3:1 to about 10:1; as previously described herein for the branched C₁₀monoolefins.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more branched C₁₀ to C₃₀ monoolefins can be reacted at a pressure offrom about 30 psig (206 kPag) to about 1,500 psig (10,300 kPag),alternatively from about 100 psig (690 kPag) to about 1,250 psig (8,600kPag), or alternatively from about 250 psig (1,700 kPag) to about 1,000psig (6,900 kPag); as previously described herein for the branched C₁₀monoolefins.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more branched C₁₀ to C₃₀ monoolefins can be reacted (as previouslydescribed herein for the branched C₁₀ monoolefins) to produce olefinconversion of equal to or greater than about 70%, alternatively equal toor greater than about 75%, or alternatively equal to or greater thanabout 80%, alternatively equal to or greater than about 85%, oralternatively equal to or greater than about 90%.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more branched C₁₀ to C₃₀ monoolefins can be reacted in the presenceof an initiating agent to produce a branched C₁₀₊ mercaptans crudecomposition; wherein the initiating agent comprises ultraviolet (UV)radiation; as previously described herein for the branched C₁₀monoolefins. In such aspect, the initiating agent can further comprise aphosphite promoter, a photoinitiator, a sulfur scavenger, anantioxidant, and the like, or combinations thereof.

In an aspect, H₂S and a feedstock comprising one or more branched C₁₀ toC₃₀ monoolefins can be reacted in the presence of UV radiation at a H₂Sto olefin molar ratio of from about 1:1 to about 15:1, alternativelyfrom about 2:1 to about 12.5:1, or alternatively from about 5:1 to about10:1; as previously described herein for the branched C₁₀ monoolefins.

In an aspect, the process can comprise reacting H₂S and a feedstockcomprising one or more branched C₁₀ to C₃₀ monoolefins in the presenceof UV radiation to produce a branched C₁₀₊ mercaptans crude composition(wherein the branched C₁₀₊ mercaptans crude composition comprises from50-100 wt. % C₁₀ to C₃₀ mercaptans, alternatively from 50-90 wt. % C₁₀to C₃₀ mercaptans, or alternatively from 75-85 wt. % C₁₀ to C₃₀mercaptans); wherein the C₁₀ to C₃₀ mercaptans present in the crudecomposition further comprise from about 70 wt. % to about 100 wt. %,alternatively from about 70 wt. % to about 95 wt. %, alternatively fromabout 80 wt. % to about 90 wt. %, or alternatively from about 79 wt. %to about 85 wt. % C₁₀ to C₃₀ primary mercaptans; from about 0 wt. % toabout 30 wt. %, alternatively from about 0 wt. % to about 20 wt. %,alternatively from about 10 wt. % to about 20 wt. %, or alternativelyfrom about 5 wt. % to about 19 wt. % C₁₀ to C₃₀ secondary mercaptans;and from about 0 wt. % to about 10 wt. %, alternatively from about 0 wt.% to about 5 wt. %, or alternatively from about 0 wt. % to about 3 wt. %C₁₀ to C₃₀ tertiary mercaptans. As will be appreciated by one of skillin the art, and with the help of this disclosure, the make-up of thebranched C₁₀₊ mercaptans crude composition, in terms of primary,secondary, and tertiary mercaptans, will depend on the make-up of thefeedstock, as well as on the reaction conditions. Further, as will beappreciated by one of skill in the art, and with the help of thisdisclosure, the make-up of each of the primary, secondary, and tertiarymercaptans will depend on the make-up of the feedstock, as well as onthe reaction conditions.

In an aspect, the C₁₀ to C₃₀ primary mercaptans can comprise a branchedC₁₀₊ mercaptan represented by Structure A-1, a branched C₁₀₊ mercaptanrepresented by Structure B-1, a branched C₁₀₊ mercaptan represented byStructure C-1, a branched C₁₀₊ mercaptan represented by Structure D-1,or combinations thereof; wherein R⁹ is a C₁ to C₂₁ alkyl group,alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁ alkylgroup, alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉alkyl group, or alternatively a C₉ to C₁₇ alkyl group.

The C₁₀ to C₃₀ primary mercaptans can further comprise a linear C₁₀₊mercaptan represented by Structure M-1; wherein R⁹ is a C₁ to C₂₁ alkylgroup, alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁alkyl group, alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇to C₁₉ alkyl group, or alternatively a C₉ to C₁₇ alkyl group.

In aspects where R⁹ is a methyl group, the C₁₀ to C₃₀ primary mercaptanscomprise one or more branched primary C₁₀ mercaptans, as previouslydisclosed herein. The branched primary C₁₀ mercaptans can comprise5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D), or combinationsthereof. Primary C₁₀ mercaptans can further comprise 1-mercapto-decane(represented by Structure M), as disclosed herein.

In an aspect, the C₁₀ to C₃₀ secondary mercaptans can comprise abranched C₁₀₊ mercaptan represented by Structure E-1, a branched C₁₀₊mercaptan represented by Structure F-1, a branched C₁₀₊ mercaptanrepresented by Structure G-1, or combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

The C₁₀ to C₃₀ secondary mercaptans can further comprise a linear C₁₀₊mercaptan represented by Structure N-1, a linear C₁₀₊ mercaptanrepresented by Structure O-1, a linear C₁₀₊ mercaptan represented byStructure P-1, or combinations thereof; wherein R⁹ is a C₁ to C₂₁ alkylgroup, alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁alkyl group, alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇to C₁₉ alkyl group, or alternatively a C₉ to C₁₇ alkyl group.

In aspects where R⁹ is a methyl group, the C₁₀ to C₃₀ secondarymercaptans comprise one or more branched secondary C₁₀ mercaptans, aspreviously disclosed herein. The branched secondary C₁₀ mercaptans cancomprise 5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G), or combinationsthereof. Secondary C₁₀ mercaptans can further comprise 4-mercapto-decane(represented by Structure N), 5-mercapto-decane (represented byStructure O), 2-mercapto-decane (represented by Structure P), orcombinations thereof; as disclosed herein.

In an aspect, the C₁₀ to C₃₀ tertiary mercaptans can comprise equal toor greater than about 90 wt. %, alternatively equal to or greater thanabout 95 wt. %, or alternatively equal to or greater than about 99 wt. %of a branched C₁₀₊ mercaptan represented by Structure H-1; wherein R⁹ isa C₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In aspects where R⁹ is a methyl group, the C₁₀ to C₃₀ tertiarymercaptans comprise one or more branched tertiary C₁₀ mercaptans, aspreviously disclosed herein. The branched tertiary C₁₀ mercaptans cancomprise 5-methyl-5-mercapto-nonane (represented by Structure H), asdisclosed herein.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more branched C₁₀ to C₃₀ monoolefins can be reacted in the presenceof an initiating agent to produce a branched C₁₀₊ mercaptans crudecomposition; wherein the initiating agent comprises an acid catalyst; aspreviously described herein for the branched C₁₀ monoolefins.

In an aspect, H₂S and a feedstock comprising one or more branched C₁₀ toC₃₀ monoolefins can be reacted in the presence of an acid catalyst at aH₂S to olefin molar ratio of from about 1:1 to about 10:1, alternativelyfrom about 2:1 to about 7.5:1, or alternatively from about 2.5:1 toabout 5:1; as previously described herein for the branched C₁₀monoolefins.

In an aspect, the process can comprise reacting H₂S and a feedstockcomprising one or more branched C₁₀ to C₃₀ monoolefins in the presenceof an acid catalyst to produce a branched C₁₀₊ mercaptans crudecomposition (wherein the branched C₁₀₊ mercaptans crude compositioncomprises from 50-100 wt. % C₁₀ to C₃₀ mercaptans, alternatively from50-90 wt. % C₁₀ to C₃₀ mercaptans, or alternatively from 75-85 wt. % C₁₀to C₃₀ mercaptans); wherein the C₁₀ to C₃₀ mercaptans comprise fromabout 0 wt. % to about 5 wt. % alternatively from about 0.1 wt. % toabout 4 wt. %, or alternatively from about 0.5 wt. % to about 2.5 wt. %C₁₀ to C₃₀ primary mercaptans; from about 80 wt. % to about 95 wt. %,alternatively from about 82.5 wt. % to about 92.5 wt. %, oralternatively from about 85 wt. % to about 90 wt. % C₁₀ to C₃₀ secondarymercaptans; and from about 5 wt. % to about 20 wt. %, alternatively fromabout 7.5 wt. % to about 17.5 wt. %, or alternatively from about 10 wt.% to about 15 wt. % C₁₀ to C₃₀ tertiary mercaptans.

In an aspect, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more branched C₁₀ to C₃₀ monoolefins can be reacted in the presenceof an initiating agent to produce a branched C₁₀₊ mercaptans crudecomposition; wherein the initiating agent comprises ahydrodesulfurization (HDS) catalyst; as previously described herein forthe branched C₁₀ monoolefins.

In an aspect, H₂S and a feedstock comprising one or more branched C₁₀ toC₃₀ monoolefins can be reacted in the presence of an HDS catalyst at aH₂S to olefin molar ratio of from about 1:1 to about 10:1, alternativelyfrom about 2:1 to about 7.5:1, or alternatively from about 2.5:1 toabout 5:1; as previously described herein for the branched C₁₀monoolefins.

In an aspect, the process can comprise reacting H₂S and a feedstockcomprising one or more branched C₁₀ to C₃₀ monoolefins in the presenceof an HDS catalyst to produce a branched C₁₀₊ mercaptans crudecomposition (wherein the branched C₁₀₊ mercaptans crude compositioncomprises from 50-100 wt. % C₁₀ to C₃₀ mercaptans, alternatively from50-90 wt. % C₁₀ to C₃₀ mercaptans, or alternatively from 75-85 wt. % C₁₀to C₃₀ mercaptans); wherein the C₁₀ to C₃₀ mercaptans comprise fromabout 5 wt. % to about 30 wt. % alternatively from about 10 wt. % toabout 25 wt. %, or alternatively from about 15 wt. % to about 20 wt. %C₁₀ to C₃₀ primary mercaptans; from about 60 wt. % to about 75 wt. %,alternatively from about 62.5 wt. % to about 72.5 wt. %, oralternatively from about 65 wt. % to about 70 wt. % C₁₀ to C₃₀ secondarymercaptans; and from about 5 wt. % to about 15 wt. %, alternatively fromabout 7.5 wt. % to about 13.5 wt. %, or alternatively from about 9 wt. %to about 12 wt. % C₁₀ to C₃₀ tertiary mercaptans.

As noted previously, any suitable feedstocks comprising one or morebranched C₁₀ to C₃₀ monoolefins can be reacted with a sulfur source(e.g., H₂S) in the presence of an initiating agent to produce a branchedC₁₀₊ mercaptans crude composition, and the branched C₁₀₊ mercaptanscrude composition can be further refined (e.g., distilled or otherwiseseparated into one or more fractions such as lights, intermediate, andheavies) to yield various compositions described herein. As described inmore detail herein, the type and/or amounts of the constituentcomponents that form the branched C₁₀₊ mercaptans crude composition canvary depending upon the feedstock (e.g., the amount and types of olefinstherein), the reaction conditions, the catalysts employed, etc., and oneskilled in the art can tailor the post reactor processing of thebranched C₁₀₊ mercaptans crude composition to account for the specificcompounds present in a given branched C₁₀₊ mercaptans crude compositionto yield various desired products and compositions of the typesdescribed herein.

Upon completion of the reaction of a feedstock comprising one or morebranched C₁₀ to C₃₀ monoolefins with a sulfur source (e.g., H₂S), areactor effluent can be recovered from the reactor and sulfur source(e.g., H₂S) removed therefrom to yield a branched C₁₀₊ mercaptans crudecomposition; as previously described herein for the branched C₁₀monoolefins. The term “branched C₁₀₊ mercaptans crude composition” or“branched C₁₀₊ mercaptans crude product” refers to an unrefined effluentstream recovered from the reactor after removal of the sulfur source(e.g., H₂S), and in particular to a sulfur source-free effluent streamthat has not undergone any additional post-reactor processing such asflashing, distillation, or other separation techniques or processes toremove any components from the effluent stream other than the initialremoval of the sulfur source.

The branched C₁₀₊ mercaptans crude composition comprises branched C₁₀ toC₃₀ mercaptans and branched C₂₀ to C₆₀ sulfides formed by the reactionof H₂S and the one or more branched C₁₀ to C₃₀ monoolefins, and thestructures of these branched C₁₀ to C₃₀ mercaptans and branched C₂₀ toC₆₀ sulfides are described in more detail herein. In addition tobranched C₁₀ to C₃₀ mercaptans and branched C₂₀ to C₆₀ sulfides, thebranched C₁₀₊ mercaptans crude composition can comprise a number ofother compounds such as unreacted olefins, inert compounds (e.g.,alkanes), non-branched C₁₀ to C₃₀ mercaptans, non-branched C₂₀ to C₆₀sulfides, non-C₁₀ to C₃₀ mercaptans (e.g., C⁹⁻ mercaptans), non-C₂₀ toC₆₀ sulfides (e.g., C¹⁹⁻ sulfides), and other impurities. Theconstituent components contained within the branched C₁₀₊ mercaptanscrude composition can vary depending upon the composition of thefeedstock (e.g., an unpurified first C₁₀ to C₃₀ feedstock as compared toa purified second C₁₀ to C₃₀ feedstock as described herein) as well asreaction conditions, catalyst, etc. In various aspects, a branched C₁₀₊mercaptans crude composition can comprise light, intermediate, and heavyfractions as described herein.

In an aspect, the branched C₁₀₊ mercaptans crude composition can containa variety of other non-C₁₀ to C₃₀ mercaptans and non-C₂₀ to C₆₀ sulfidescomponents (e.g., impurities) such as C₈ mercaptans; C₁₆ to C₁₉ sulfidesrepresented by the structure R¹²—S—R¹³, wherein R¹² and R¹³ are eachindependently a functional group derived from a C₈₊ monoolefin, whereinR¹² and R¹³ are not both derived from a branched C₁₀₊ monoolefin;unreacted C₈₊ monoolefins; non-olefin impurities selected from the groupconsisting of C₈₋₁₄ alkanes, cyclohexane, methylcyclopentane,methylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene,hexamethylbenzene, C₄₋₁₂ alcohols, 2-ethyl-1-hexanol, and2-ethylhexyl-2-ethylhexanoate; and combinations thereof.

In an aspect, a process of the present disclosure can further compriserecovering a reaction product from the branched C₁₀₊ mercaptans crudecomposition; wherein the reaction product can comprise branched C₁₀₊mercaptans and/or branched C₂₀₊ sulfides, wherein the branched C₁₀₊mercaptans comprise branched C₁₀ to C₃₀ mercaptans; and wherein thebranched C₂₀₊ sulfides comprise branched C₂₀ to C₆₀ sulfides representedby the structure R¹⁰—S—R¹¹, wherein R¹⁰ and R¹¹ are each independently afunctional group derived from an olefin, wherein the olefin comprises abranched C₁₀₊ monoolefin as disclosed herein.

In an aspect, the reaction product can comprise a branched C₁₀₊mercaptans composition (intermediate fraction; first reaction product),a branched C₂₀₊ sulfides composition (heavy fraction; second reactionproduct), a branched C₁₀₊ mercaptans/branched C₂₀₊ sulfides composition(intermediate and heavy fractions; first and second reaction products),or combinations thereof.

In an aspect, a branched C₁₀₊ mercaptans crude composition comprisingbranched C₁₀₊ mercaptans and branched C₂₀₊ sulfides as disclosed hereincan be separated into two or more fractions (e.g., light fraction,intermediate fraction, heavy fraction, etc.) by any process or unitoperation known in the art. For example, a branched C₁₀₊ mercaptanscrude composition can be processed (e.g., distilled) to remove afraction of light compounds. Alternatively, a branched C₁₀₊ mercaptanscrude composition can be processed to recover both a light fraction andan intermediate fraction (e.g., a rough cut), followed by furtherprocessing to obtain one or more fine cuts. Alternatively, a branchedC₁₀₊ mercaptans crude composition can be processed to recover a heavyfraction (e.g., a C₂₀₊ sulfides fraction). Alternatively, a branchedC₁₀₊ mercaptans crude composition can be processed to separate out anycombination of a light fraction, an intermediate fraction (e.g.,comprising C₁₀₊ mercaptans, including branched C₁₀₊ mercaptans), and aheavy fraction (e.g., comprising C₂₀₊ sulfides, including branched C₂₀₊sulfides). Furthermore, a light, intermediate or heavy fraction (e.g., arough cut) can be further processed or parsed to obtain one or moredesired fine cuts (e.g., a C₁₀ to C₃₀ mercaptan fraction).Alternatively, a branched C₁₀₊ mercaptans crude composition can beseparated to produce a high-purity C₁₀₊ mercaptan stream and/or ahigh-purity C₂₀₊ sulfide stream (e.g., to obtain a desired fine cut orfraction such as a C₁₀ to C₃₀ mercaptan fraction). Further, theseseparated streams can be blended in any combination of ratios to producea mixture with specific concentrations of one of more components (e.g.,desired blend ratios of branched C₁₀₊ mercaptans and/or branched C₂₀₊sulfides, for example to aid in a particular end use). The unitoperations/processes used for these separations are known to one ofskill and the art and include, but are not limited to, distillation,fractionation, flashing, stripping, and absorption, and others. The unitoperation conditions, such as for example, temperature, pressure, flowrates, and others at which these unit operations produce one or more ofthe desired fractions can easily be determined by one of ordinary skillin the art.

In an aspect, a light fraction is removed from the branched C₁₀₊mercaptans crude composition, for example by flashing, distillation,fractionation, stripping, absorption, etc.

In an aspect, the light fraction removed from the branched C₁₀₊mercaptans crude composition can comprise at least about 90 wt. %,alternatively at least about 92 wt. %, alternatively at least about 95wt. %, alternatively at least about 96 wt. %, alternatively at leastabout 97 wt. %, alternatively at least about 98 wt. %, alternatively atleast about 99 wt. % C⁹⁻ compounds, based on the total weight of thelight fraction. Nonlimiting examples of C⁹⁻ compounds include C⁹⁻monoolefins (e.g., unreacted C⁹⁻ monoolefins), C⁹⁻ mercaptans, C⁹⁻alkanes, cyclohexane, methylcyclopentane, methylcyclohexane, benzene,toluene, ethylbenzene, xylene, mesitylene, C⁹⁻ alcohols,2-ethyl-1-hexanol, and the like, or combinations thereof. In an aspect,the light fraction removed from the branched C₁₀₊ mercaptans crudecomposition can comprise less than about 10 wt. %, alternatively lessthan about 5 wt. %, alternatively less than about 4 wt. %, alternativelyat less than about 3 wt. %, alternatively less than about 2 wt. %,alternatively less than about 1 wt. % C₁₀₊ compounds, based on the totalweight of the light fraction.

Following removal of the lights (for example, via flashing) from thebranched C₁₀₊ mercaptans crude composition, a combined intermediate andheavy fraction (i.e., C₁₀₊ compounds sometimes referred to as a kettleproduct in the Examples) can remain, and the combined intermediate andheavy fraction can be used “as is” or can be further processed, forexample separated or split into separate intermediate and heavyfractions (and said separate intermediate and heavy fractions can besubsequently recombined in various blends and associated blend ratios),as described in more detail herein. In an aspect, a combinedintermediate and heavy fraction (i.e., C₁₀₊ compounds) formed by removalof the light fraction from the branched C₁₀₊ mercaptans crudecomposition can comprise less than about 15 wt. %, alternatively lessthan about 10 wt. %, alternatively less than about 9 wt. %,alternatively less than about 8 wt. %, alternatively less than about 7wt. %, alternatively less than about 6 wt. %, alternatively less thanabout 5 wt. %, alternatively less than about 4 wt. %, alternatively lessthan about 3 wt. %, alternatively less than about 2 wt. %, oralternatively less than about 1 wt. % C⁹⁻ products, based on the totalweight of the combined intermediate and heavy fraction (i.e., C₁₀₊compounds).

In an aspect, a combined intermediate and heavy fraction (i.e., C₁₀₊compounds) recovered from the branched C₁₀₊ mercaptans crude compositioncan comprise (A) at least about 50 wt. %, alternatively at least about60 wt. %, alternatively at least about 70 wt. %, alternatively at leastabout 80 wt. %, alternatively at least about 90 wt. %, alternatively atleast about 95 wt. %, or alternatively at least about 99 wt. %mercaptans, based on the total weight of the combined fraction; whereinat least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at leastabout 85 wt. % of the mercaptans can be branched C₁₀ to C₃₀ mercaptansselected from the group consisting of a branched C₁₀ to C₃₀ mercaptanrepresented by Structure A-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure B-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; and (B) at leastabout 10 wt. %, alternatively at least about 15 wt. %, alternatively atleast about 20 wt. %, alternatively at least about 25 wt. % sulfides, oralternatively at least about 30 wt. % sulfides; wherein at least about50 wt. %, alternatively at least about 60 wt. %, alternatively at leastabout 70 wt. %, alternatively at least about 75 wt. %, alternatively atleast about 80 wt. %, or alternatively at least about 85 wt. % of thesulfides can be branched C₂₀ to C₆₀ sulfides represented by structureR¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ can each independently be afunctional group derived from an olefin, wherein the olefin comprises abranched C₁₀ to C₃₀ monoolefin represented by Structure I-1, a branchedC₁₀ to C₃₀ monoolefin represented by Structure J-1, a branched C₁₀ toC₃₀ monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof; andwherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkylgroup, alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁alkyl group, alternatively a C₇ to C₁₉ alkyl group, or alternatively aC₉ to C₁₇ alkyl group.

In an aspect, the branched C₁₀₊ mercaptans crude composition can beflashed to remove a light fraction as described herein to produce acombined intermediate and heavy fraction (i.e., C₁₀₊ compounds)comprising: (A) at least about 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,75, 80, or 85 wt. % C₁₀₊ branched mercaptans selected from the groupconsisting of a branched C₁₀ to C₃₀ mercaptan represented by StructureA-1, a branched C₁₀ to C₃₀ mercaptan represented by Structure B-1, abranched C₁₀ to C₃₀ mercaptan represented by Structure C-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure D-1, a branched C₁₀ to C₃₀mercaptan represented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; and (B) at leastabout 5 wt. %, alternatively at least about 10 wt. %, alternatively atleast about 15 wt. %, alternatively at least about 20 wt. %,alternatively at least about 25 wt. %, or alternatively at least about30 wt. % branched C₂₀ to C₆₀ sulfides represented by structureR¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ can each independently be afunctional group derived from an olefin, wherein the olefin comprises abranched C₁₀ to C₃₀ monoolefin represented by Structure I-1, a branchedC₁₀ to C₃₀ monoolefin represented by Structure J-1, a branched C₁₀ toC₃₀ monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof; andwherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkylgroup, alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁alkyl group, alternatively a C₇ to C₁₉ alkyl group, or alternatively aC₉ to C₁₇ alkyl group.

In an aspect, the branched C₁₀₊ mercaptans crude composition can beflashed to remove a lights fraction as described herein to produce acombined intermediate and heavy fraction (i.e., C₁₀₊ compounds)comprising: (A) from at least about 50 wt. % to at least about 90 wt. %,alternatively from at least about 55 wt. % to at least about 85 wt. %,or alternatively from at least about 60 wt. % to at least about 80 wt. %mercaptans, wherein at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 75 wt. %, alternatively at least about 80 wt. %, oralternatively at least about 85 wt. % of the mercaptans can be branchedC₁₀ to C₃₀ mercaptans selected from the group consisting of a branchedC₁₀ to C₃₀ mercaptan represented by Structure A-1, a branched C₁₀ to C₃₀mercaptan represented by Structure B-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; and (B) from atleast about 10 wt. % to at least about 30 wt. %, alternatively from atleast about 10 wt. % to at least about 25 wt. %, alternatively from atleast about 12.5 wt. % to at least about 22.5 wt. %, or alternativelyfrom at least about 15 wt. % to at least about 20 wt. % sulfides;wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at leastabout 85 wt. % of the sulfides can be branched C₂₀ to C₆₀ sulfidesrepresented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ can eachindependently be a functional group derived from an olefin, wherein theolefin comprises a branched C₁₀ to C₃₀ monoolefin represented byStructure I-1, a branched C₁₀ to C₃₀ monoolefin represented by StructureJ-1, a branched C₁₀ to C₃₀ monoolefin represented by Structure K-1, abranched C₁₀ to C₃₀ monoolefin represented by Structure L-1, orcombinations thereof; and wherein R⁹ is a C₁ to C₂₁ alkyl group,alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁ alkylgroup, alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉alkyl group, or alternatively a C₉ to C₁₇ alkyl group.

In an aspect, the branched C₁₀₊ mercaptans crude composition can beflashed to remove a light fraction and subsequently further separated toproduce an intermediate fraction and a heavy fraction (i.e., C₁₀₊compounds). The intermediate fraction and the heavy fractions recoveredfrom the branched C₁₀₊ mercaptans crude composition can then beoptionally further processed (e.g., polished) and mixed in anyappropriate ratio to produce blended compositions, as previouslydescribed herein for crude compositions derived from branched C₁₀monoolefins.

In an aspect, an intermediate fraction recovered from the branched C₁₀₊mercaptans crude composition can comprise at least about 25 wt. %,alternatively at least about 30 wt. %, alternatively at least about 40wt. %, alternatively at least about 50 wt. %, alternatively at leastabout 75 wt. %, or alternatively at least about 85 wt. % C₁₀₊mercaptans, based on the total weight of the intermediate fraction,wherein the C₁₀₊ mercaptans are branched C₁₀ to C₃₀ mercaptans asdisclosed herein.

In an aspect, the heavy fraction recovered from the branched C₁₀₊mercaptans crude composition can comprise at least about 5, 10, 15, 20,25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt. %, C₂₀₊sulfides, based on the total weight of the heavy fraction, wherein theC₂₀₊ sulfides are branched C₂₀ to C₆₀ sulfides as disclosed herein.

In an aspect, the branched C₁₀₊ mercaptans crude composition can beseparated into light, intermediate, and heavy fractions by distillation,for example in a single distillation column having a light fractionrecovered as an overhead stream, an intermediate fraction (e.g.,comprising C₁₀₊ compounds, including branched C₁₀₊ mercaptans) recoveredas a side stream, and a heavy fraction (e.g., comprising C₂₀₊ compounds,including branched C₂₀₊ sulfides) recovered as a bottom stream. Inalternative aspects, the separation can be in sequential steps such asremoval of the lights fraction in a first distillation column, followedby separation of the intermediate fraction (e.g., comprising C₁₀₊compounds, including branched C₁₀₊ mercaptans) as an overhead stream ina second distillation column and the heavy fraction (e.g., comprisingC₂₀₊ compounds, including branched C₂₀₊ sulfides) as a bottom stream ofthe second distillation column. These “rough-cut” light, intermediate,and heavy streams can be used “as is” or they can be further processed(e.g., further refined or polished, for example by additionaldistillation or other separation techniques to produce “fine-cuts”)and/or blended to obtain a variety of products that are salable orotherwise available for a variety of end uses such as mining orecollector compositions or chain transfer agents. For example, a varietyof C₁₀₊ mercaptans compositions, C₂₀₊ sulfides compositions, and mixedC₁₀₊ mercaptans/C₂₀₊ sulfides compositions can be produced of the typedisclosed in more detail herein.

In aspects where the olefin feedstock (e.g., olefin feedstock reactedwith a sulfur source (e.g., H₂S) in the presence of an initiating agentto produce the branched C₁₀₊ mercaptans crude composition) comprises C₁₀to C₁₉ monoolefins, the intermediate fraction comprises C₁₀ to C₁₉mercaptans, and the heavy fraction comprises C₂₀ to C₃₈ sulfides.

In aspects where the olefin feedstock (e.g., olefin feedstock reactedwith a sulfur source (e.g., H₂S) in the presence of an initiating agentto produce the branched C₁₀₊ mercaptans crude composition) comprises C₂₀to C₃₀ monoolefins, the intermediate fraction comprises C₂₀ to C₃₀mercaptans, and the heavy fraction comprises C₄₀ to C₆₀ sulfides.

In aspects where the olefin feedstock (e.g., olefin feedstock reactedwith a sulfur source (e.g., H₂S) in the presence of an initiating agentto produce the branched C₁₀₊ mercaptans crude composition) comprises C₁₀to C₃₀ monoolefins, the intermediate and heavy fractions recovered bydistillation can comprise mercaptans and sulfides as follows. In someaspects, the intermediate fraction can comprise C₁₀ to C₁₉ mercaptans,and the heavy fraction can comprise C₂₀ to C₃₀ mercaptans and C₂₀ to C₆₀sulfides. In other aspects, intermediate fraction can comprise C₁₀ toC₃₀ mercaptans and C₂₀ to C₃₀ sulfides, and the heavy fraction cancomprise C₃₁ to C₆₀ sulfides. In yet other aspects, a first intermediatefraction can comprise C₁₀ to C₁₉ mercaptans, a second intermediatefraction can comprise C₂₀ to C₃₀ mercaptans and C₂₀ to C₃₀ sulfides, andthe heavy fraction can comprise C₃₁ to C₆₀ sulfides. Intermediate andheavy fractions comprising both mercaptans and sulfides could be used asrecovered (e.g., mixed mercaptans/sulfides compositions), or can befurther processed to separate and recover further mercaptan compositionsand sulfide compositions.

In an aspect, an intermediate fraction can comprise at least about 25wt. %, alternatively at least about 30 wt. %, alternatively at leastabout 40 wt. %, alternatively at least about 50 wt. %, alternatively atleast about 75 wt. %, or alternatively at least about 85 wt. % branchedC₁₀, mercaptans. In such aspect, the branched C₁₀, mercaptans can beselected from the group consisting of a branched C₁₀ to C₃₀ mercaptanrepresented by Structure A-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure B-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In an aspect, the heavy fraction can comprise at least about 5, 10, 15,20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt. % branchedC₂₀₊ sulfides represented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ andR¹¹ can each independently be a branched C₁₀ to C₃₀ alkyl group derivedfrom a branched C₁₀ to C₃₀ monoolefin, and wherein the branched C₁₀ toC₃₀ alkyl group is selected from the group consisting of

wherein * designates the attachment point to the S atom of the branchedC₂₀₊ sulfide; and wherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively aC₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁ alkyl group,alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉ alkylgroup, or alternatively a C₉ to C₁₇ alkyl group.

In an aspect, a C₁₀₊ mercaptans composition can comprise C₁₀₊mercaptans, wherein at least a portion of the C₁₀₊ mercaptans comprisebranched C₁₀ to C₃₀ mercaptans. In an aspect, the branched C₁₀ to C₃₀mercaptans can comprise a branched C₁₀ to C₃₀ mercaptan represented byStructure A-1, a branched C₁₀ to C₃₀ mercaptan represented by StructureB-1, a branched C₁₀ to C₃₀ mercaptan represented by Structure C-1, abranched C₁₀ to C₃₀ mercaptan represented by Structure D-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure E-1, a branched C₁₀ to C₃₀mercaptan represented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, or combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group. For purposes of the disclosure herein, branched C₁₀₊mercaptans refer to mercaptans (or thiols) that are characterized by thegeneral formula R¹⁴—SH, wherein R¹⁴ is a branched alkyl group (asopposed to a linear alkyl group), i.e., an alkyl group substituted withalkyl substituents; and wherein R¹⁴ has from 10 to 30 carbon atoms,alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30carbon atoms, alternatively from 14 to 30 carbon atoms, alternativelyfrom 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.Further, for purposes of the disclosure herein, a composition comprisingmercaptans, wherein at least a portion of the mercaptans are branchedC₁₀₊ mercaptans (e.g., branched C₁₀ to C₃₀ mercaptans as disclosedherein), can also be referred to as a “branched C₁₀₊ mercaptanscomposition.” In an aspect, the C₁₀₊ mercaptans composition can compriseany suitable amount of branched C₁₀ to C₃₀ mercaptans.

In an aspect, the C₁₀₊ mercaptans can further comprise non-branched C₁₀₊mercaptans, such as for example a linear C₁₀ to C₃₀ mercaptanrepresented by Structure M-1, a linear C₁₀ to C₃₀ mercaptan representedby Structure N-1, a linear C₁₀ to C₃₀ mercaptan represented by StructureO-1, a linear C₁₀ to C₃₀ mercaptan represented by Structure P-1, orcombinations thereof; wherein R⁹ is a C₁ to C₂₁ alkyl group,alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁ alkylgroup, alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉alkyl group, or alternatively a C₉ to C₁₇ alkyl group.

In aspects where R⁹ is a methyl group, the C₁₀₊ mercaptans can furthercomprise non-branched C₁₀ mercaptans, as previously disclosed herein.The non-branched C₁₀ mercaptans can comprise 1-mercapto-decane(represented by Structure M), 4-mercapto-decane (represented byStructure N), 5-mercapto-decane (represented by Structure O),2-mercapto-decane (represented by Structure P), or combinations thereof.

In some aspects, a C₁₀₊ mercaptans composition can comprise at leastabout 50 wt. %, alternatively at least about 60 wt. %, alternatively atleast about 70 wt. %, alternatively at least about 80 wt. %,alternatively at least about 90 wt. %, alternatively at least about 95wt. %, or alternatively at least about 99 wt. % C₁₀₊ mercaptans, basedon the total weight of the C₁₀₊ mercaptans composition; wherein at leastabout 50 wt. %, alternatively at least about 60 wt. %, alternatively atleast about 70 wt. %, alternatively at least about 75 wt. %,alternatively at least about 80 wt. %, or alternatively at least 85 wt.% of the C₁₀₊ mercaptans can be branched C₁₀ to C₃₀ mercaptanscharacterized by the general formula R¹⁴—SH, wherein R¹⁴ is a branchedalkyl group; and wherein R¹⁴ has from 10 to 30 carbon atoms,alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30carbon atoms, alternatively from 14 to 30 carbon atoms, alternativelyfrom 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.In such aspects, the branched C₁₀ to C₃₀ mercaptans characterized by thegeneral formula R¹⁴—SH can be selected from the group consisting of abranched C₁₀ to C₃₀ mercaptan represented by Structure A-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure B-1, a branched C₁₀ to C₃₀mercaptan represented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In other aspects, a C₁₀₊ mercaptans composition can comprise at leastabout 1 wt. %, alternatively at least about 5 wt. %, alternatively atleast about 10 wt. %, alternatively at least about 20 wt. %,alternatively at least about 30 wt. %, alternatively at least about 40wt. %, alternatively at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 80 wt. %, alternatively at least about 90 wt. %,alternatively at least about 95 wt. %, or alternatively at least about99 wt. % mercaptans, wherein at least a portion of the mercaptans can bebranched C₁₀ to C₃₀ mercaptans characterized by the general formulaR¹⁴—SH, wherein R¹⁴ is a branched alkyl group; and wherein R¹⁴ has from10 to 30 carbon atoms, alternatively from 11 to 30 carbon atoms,alternatively from 12 to 30 carbon atoms, alternatively from 14 to 30carbon atoms, alternatively from 16 to 28 carbon atoms, or alternativelyfrom 18 to 26 carbon atoms. In such aspects, the branched C₁₀ to C₃₀mercaptans characterized by the general formula R¹⁴—SH can be selectedfrom the group consisting of a branched C₁₀ to C₃₀ mercaptan representedby Structure A-1, a branched C₁₀ to C₃₀ mercaptan represented byStructure B-1, a branched C₁₀ to C₃₀ mercaptan represented by StructureC-1, a branched C₁₀ to C₃₀ mercaptan represented by Structure D-1, abranched C₁₀ to C₃₀ mercaptan represented by Structure E-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure F-1, a branched C₁₀ to C₃₀mercaptan represented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In yet other aspects, a C₁₀₊ mercaptans composition can comprise atleast about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 80wt. %, alternatively at least about 90 wt. %, alternatively at leastabout 95 wt. %, or alternatively at least about 99 wt. % mercaptans;wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at least85 wt. % of the mercaptans can be branched C₁₀ to C₃₀ mercaptanscharacterized by the general formula R¹⁴—SH, wherein R¹⁴ is a branchedalkyl group; and wherein R¹⁴ has from 10 to 30 carbon atoms,alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30carbon atoms, alternatively from 14 to 30 carbon atoms, alternativelyfrom 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.In such aspects, the branched C₁₀ to C₃₀ mercaptans characterized by thegeneral formula R¹⁴—SH can be selected from the group consisting of abranched C₁₀ to C₃₀ mercaptan represented by Structure A-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure B-1, a branched C₁₀ to C₃₀mercaptan represented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In still yet other aspects, a C₁₀₊ mercaptans composition can compriseat least about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt. %mercaptans; wherein at least about 25, 30, 35, 40, 45, 50, 55, 60, 65,70, 75, 80, 85, 90, 95, or 99 wt. % of the mercaptans can be branchedC₁₀ to C₃₀ mercaptans characterized by the general formula R¹⁴—SH,wherein R¹⁴ is a branched alkyl group; and wherein R¹⁴ has from 10 to 30carbon atoms, alternatively from 11 to 30 carbon atoms, alternativelyfrom 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms,alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26carbon atoms. In such aspects, the branched C₁₀ to C₃₀ mercaptanscharacterized by the general formula R¹⁴—SH can be selected from thegroup consisting of a branched C₁₀ to C₃₀ mercaptan represented byStructure A-1, a branched C₁₀ to C₃₀ mercaptan represented by StructureB-1, a branched C₁₀ to C₃₀ mercaptan represented by Structure C-1, abranched C₁₀ to C₃₀ mercaptan represented by Structure D-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure E-1, a branched C₁₀ to C₃₀mercaptan represented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In still yet other aspects, a C₁₀₊ mercaptans composition can comprisefrom at least about 50 wt. % to at least about 90 wt. %, alternativelyfrom at least about 55 wt. % to at least about 85 wt. %, oralternatively from at least about 60 wt. % to at least about 80 wt. %mercaptans, wherein at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 75 wt. %, alternatively at least about 80 wt. %, oralternatively at least about 85 wt. % of the mercaptans can be branchedC₁₀ to C₃₀ mercaptans characterized by the general formula R¹⁴—SH,wherein R¹⁴ is a branched alkyl group; and wherein R¹⁴ has from 10 to 30carbon atoms, alternatively from 11 to 30 carbon atoms, alternativelyfrom 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms,alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26carbon atoms. In such aspects, the branched C₁₀ to C₃₀ mercaptanscharacterized by the general formula R¹⁴—SH can be selected from thegroup consisting of a branched C₁₀ to C₃₀ mercaptan represented byStructure A-1, a branched C₁₀ to C₃₀ mercaptan represented by StructureB-1, a branched C₁₀ to C₃₀ mercaptan represented by Structure C-1, abranched C₁₀ to C₃₀ mercaptan represented by Structure D-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure E-1, a branched C₁₀ to C₃₀mercaptan represented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In still yet other aspects, a C₁₀₊ mercaptans composition can consist ofor consist essentially of branched C₁₀ to C₃₀ mercaptans characterizedby the general formula R¹⁴—SH, wherein R¹⁴ is a branched alkyl group;and wherein R¹⁴ has from 10 to 30 carbon atoms, alternatively from 11 to30 carbon atoms, alternatively from 12 to 30 carbon atoms, alternativelyfrom 14 to 30 carbon atoms, alternatively from 16 to 28 carbon atoms, oralternatively from 18 to 26 carbon atoms. In such aspects, the branchedC₁₀ to C₃₀ mercaptans characterized by the general formula R¹⁴—SH can beselected from the group consisting of a branched C₁₀ to C₃₀ mercaptanrepresented by Structure A-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure B-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In still yet other aspects, a C₁₀₊ mercaptans composition can compriseat least about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,75, 80, 85, 90, 95, or 99 wt. % branched C₁₀ to C₃₀ mercaptanscharacterized by the general formula R¹⁴—SH, wherein R¹⁴ is a branchedalkyl group; and wherein R¹⁴ has from 10 to 30 carbon atoms,alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30carbon atoms, alternatively from 14 to 30 carbon atoms, alternativelyfrom 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.In such aspects, the branched C₁₀ to C₃₀ mercaptans characterized by thegeneral formula R¹⁴—SH can be selected from the group consisting of abranched C₁₀ to C₃₀ mercaptan represented by Structure A-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure B-1, a branched C₁₀ to C₃₀mercaptan represented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In still yet other aspects, a C₁₀₊ mercaptans composition can comprisemercaptans, wherein at least about 50, 55, 60, 65, 70, 75, 80, 85, 90,95, or 99 wt. % of the mercaptans are branched C₁₀ to C₃₀ mercaptanscharacterized by the general formula R¹⁴—SH, wherein R¹⁴ is a branchedalkyl group; and wherein R¹⁴ has from 10 to 30 carbon atoms,alternatively from 11 to 30 carbon atoms, alternatively from 12 to 30carbon atoms, alternatively from 14 to 30 carbon atoms, alternativelyfrom 16 to 28 carbon atoms, or alternatively from 18 to 26 carbon atoms.In such aspects, the branched C₁₀ to C₃₀ mercaptans characterized by thegeneral formula R¹⁴—SH can be selected from the group consisting of abranched C₁₀ to C₃₀ mercaptan represented by Structure A-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure B-1, a branched C₁₀ to C₃₀mercaptan represented by Structure C-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure D-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure E-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure F-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; wherein R⁹ is aC₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group,alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkylgroup, alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ toC₁₇ alkyl group.

In an aspect, a C₂₀₊ sulfides composition can comprise sulfides, whereinat least a portion of the sulfides comprise C₂₀₊ sulfides, and whereinat least a portion of the C₂₀₊ sulfides comprise branched C₂₀ to C₆₀sulfides represented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹can each independently be an alkyl group, and wherein at least a portionof the alkyl groups comprises a branched C₁₀ to C₃₀ alkyl group,alternatively a branched C₁₁ to C₃₀ alkyl group, alternatively abranched C₁₂ to C₃₀ alkyl group, alternatively a branched C₁₄ to C₃₀alkyl group, alternatively a branched C₁₆ to C₂₈ alkyl group, oralternatively a branched C₁₈ to C₂₆ alkyl group. In such aspect, thealkyl group (e.g., a branched C₁₀ to C₃₀ alkyl group as R¹⁰, R¹¹) cancomprise a functional group derived from an olefin, wherein the olefincomprises a branched C₁₀ to C₃₀ monoolefin represented by Structure I-1,a branched C₁₀ to C₃₀ monoolefin represented by Structure J-1, abranched C₁₀ to C₃₀ monoolefin represented by Structure K-1, a branchedC₁₀ to C₃₀ monoolefin represented by Structure L-1, or combinationsthereof; wherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively a C₂ toC₂₁ alkyl group, alternatively a C₃ to C₂₁ alkyl group, alternatively aC₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉ alkyl group, oralternatively a C₉ to C₁₇ alkyl group. As previously disclosed herein,for purposes of the disclosure herein a sulfide (e.g., a branched C₂₀ toC₆₀ sulfide) will be referred to by the total number of carbon atoms (asopposed to the number of carbons of only one of the alkyl groups presentin a dialkyl sulfide). For example, a H₂₁C₁₀—S—C₁₀H₂₁ sulfide will bereferred to as a C₂₀ sulfide (rather than a C₁₀ sulfide); aH₂₅C₁₂—S—C₁₄H₂₉ sulfide will be referred to as a C₂₆ sulfide (ratherthan a C₁₂ sulfide or a C₁₄ sulfide); a H₄₅C₂₂—S—C₂₂H₄₅ sulfide will bereferred to as a C₄₄ sulfide (rather than a C₂₂ sulfide); etc. Forpurposes of the disclosure herein, branched C₂₀ to C₆₀ sulfides refer tosulfides (or thioethers) that are characterized by the general formulaR¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ are each independently a branchedC₁₀ to C₃₀ alkyl group, alternatively a branched C₁₁ to C₃₀ alkyl group,alternatively a branched C₁₂ to C₃₀ alkyl group, alternatively abranched C₁₄ to C₃₀ alkyl group, alternatively a branched C₁₆ to C₂₈alkyl group, or alternatively a branched C₁₈ to C₂₆ alkyl group (asopposed to a linear alkyl group), i.e., an alkyl group substituted withalkyl substituents. Stated alternatively, branched C₂₀ to C₆₀ sulfidesrefer to sulfides wherein both R¹⁰ and R¹¹ are branched C₁₀ to C₃₀ alkylgroups, wherein R¹⁰ and R¹¹ can be the same or different. Further, forpurposes of the disclosure herein, a composition comprising sulfides,wherein at least a portion of the sulfides are branched C₂₀ to C₆₀sulfides represented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹are each independently an alkyl group, wherein the alkyl group comprisesa branched C₁₀ to C₃₀ alkyl group (e.g., a functional group derived froman olefin, and wherein the olefin comprises a branched C₁₀ to C₃₀monoolefin as disclosed herein), can also be referred to as a “branchedC₂₀₊ sulfides composition.” In an aspect, the C₂₀₊ sulfides compositioncan comprise any suitable amount of branched C₂₀ to C₆₀ sulfides.

In an aspect, a C₂₀₊ sulfides composition can comprise sulfides, whereinat least a portion of the sulfides comprise C₂₀₊ sulfides, and whereinat least a portion of the C₂₀₊ sulfides comprise branched C₂₀ to C₆₀sulfides represented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹can each independently be a branched C₁₀ to C₃₀ alkyl group derived froma branched C₁₀ to C₃₀ monoolefin, and wherein the branched C₁₀ to C₃₀alkyl group is selected from the group consisting of

wherein * designates the attachment point to the S atom of the branchedC₂₀ to C₆₀ sulfide; and wherein R⁹ is a C₁ to C₂₁ alkyl group,alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁ alkylgroup, alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉alkyl group, or alternatively a C₉ to C₁₇ alkyl group. In an aspect, thebranched C₁₀ to C₃₀ monoolefin can comprise a branched C₁₀ to C₃₀monoolefin represented by Structure I-1, a branched C₁₀ to C₃₀monoolefin represented by Structure J-1, a branched C₁₀ to C₃₀monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof.

In an aspect, the C₂₀ to C₆₀ sulfides can further comprise non-branchedC₂₀ to C₆₀ sulfides and/or partially branched C₂₀ to C₆₀ sulfidesrepresented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ (in thecase of non-branched C₂₀ to C₆₀ sulfides) or one of the R¹⁰ and R¹¹ (inthe case of partially-branched C₂₀ to C₆₀ sulfides) can be a linear C₁₀to C₃₀ alkyl group derived from a linear C₁₀ to C₃₀ monoolefin, such asfor example a linear C₁₀ to C₃₀ monoolefin represented by Structure Q-1,a linear C₁₀ to C₃₀ monoolefin represented by Structure R-1, a linearC₁₀ to C₃₀ monoolefin represented by Structure S-1, or combinationsthereof; wherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively a C₂ toC₂₁ alkyl group, alternatively a C₃ to C₂₁ alkyl group, alternatively aC₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉ alkyl group, oralternatively a C₉ to C₁₇ alkyl group.

For purposes of the disclosure herein, the non-branched C₂₀ to C₆₀sulfides represented by structure R¹⁰—S—R¹¹ are the sulfides whereinboth R¹⁰ and R¹¹ are each independently a linear C₁₀ to C₃₀ alkyl groupderived from a linear C₁₀ to C₃₀ monoolefin. Further, for purposes ofthe disclosure herein, the partially branched C₂₀ to C₆₀ sulfidesrepresented by structure R¹⁰—S—R¹¹ are the sulfides wherein one of theR¹⁰ and R¹¹ is a linear C₁₀ to C₃₀ alkyl group derived from a linear C₁₀to C₃₀ monoolefin, while the other one of the R¹⁰ and R¹¹ is a branchedC₁₀ to C₃₀ alkyl group derived from a branched C₁₀ to C₃₀ monoolefin asdescribed herein.

In aspects where R⁹ is a methyl group, the linear C₁₀ to C₃₀ monoolefincan further comprise linear C₁₀ monoolefins, as previously disclosedherein. The linear C₁₀ monoolefins can comprise 4-decene (represented byStructure Q), 5-decene (represented by Structure R), 1-decene(represented by Structure S), or combinations thereof.

In some aspects, a C₂₀₊ sulfides composition can comprise sulfides,wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 80wt. %, alternatively at least about 90 wt. %, alternatively at leastabout 95 wt. %, or alternatively at least about 99 wt. % of the sulfidescan be branched C₂₀ to C₆₀ sulfides represented by structure R¹⁰—S—R¹¹,wherein both R¹⁰ and R¹¹ can each independently be a functional groupderived from an olefin, and wherein the olefin comprises a branched C₁₀to C₃₀ monoolefin, alternatively a branched C₁₁ to C₃₀ monoolefin,alternatively a branched C₁₂ to C₃₀ monoolefin, alternatively a branchedC₁₄ to C₃₀ monoolefin, alternatively a branched C₁₆ to C₂₈ monoolefin,or alternatively a branched C₁₈ to C₂₆ monoolefin. In such aspects, theolefin can comprise a branched C₁₀ to C₃₀ monoolefin represented byStructure I-1, a branched C₁₀ to C₃₀ monoolefin represented by StructureJ-1, a branched C₁₀ to C₃₀ monoolefin represented by Structure K-1, abranched C₁₀ to C₃₀ monoolefin represented by Structure L-1, orcombinations thereof.

In other aspects, a C₂₀₊ sulfides composition can comprise at leastabout 1 wt. %, alternatively at least about 5 wt. %, alternatively atleast about 10 wt. %, alternatively at least about 20 wt. %,alternatively at least about 30 wt. %, alternatively at least about 40wt. %, alternatively at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 80 wt. %, alternatively at least about 90 wt. %,alternatively at least about 95 wt. %, or alternatively at least about99 wt. % sulfides, wherein at least a portion of the sulfides can bebranched C₂₀ to C₆₀ sulfides represented by structure R¹⁰—S—R¹¹, whereinboth R¹⁰ and R¹¹ can each independently be a functional group derivedfrom an olefin, and wherein the olefin comprises a branched C₁₀ to C₃₀monoolefin, alternatively a branched C₁₁ to C₃₀ monoolefin,alternatively a branched C₁₂ to C₃₀ monoolefin, alternatively a branchedC₁₄ to C₃₀ monoolefin, alternatively a branched C₁₆ to C₂₈ monoolefin,or alternatively a branched C₁₈ to C₂₆ monoolefin. In such aspects, theolefin can comprise a branched C₁₀ to C₃₀ monoolefin represented byStructure I-1, a branched C₁₀ to C₃₀ monoolefin represented by StructureJ-1, a branched C₁₀ to C₃₀ monoolefin represented by Structure K-1, abranched C₁₀ to C₃₀ monoolefin represented by Structure L-1, orcombinations thereof.

In other aspects, a C₂₀₊ sulfides composition can comprise at leastabout 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,85, 90, 95, or 99 wt. %, sulfides, wherein at least about 1, 5, 10, 15,20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99wt. % of the sulfides can be branched C₂₀ to C₆₀ sulfides represented bystructure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ can each independently bea functional group derived from an olefin, and wherein the olefincomprises a branched C₁₀ to C₃₀ monoolefin, alternatively a branched C₁₁to C₃₀ monoolefin, alternatively a branched C₁₂ to C₃₀ monoolefin,alternatively a branched C₁₄ to C₃₀ monoolefin, alternatively a branchedC₁₆ to C₂₈ monoolefin, or alternatively a branched C₁₈ to C₂₆monoolefin. In such aspects, the olefin can comprise a branched C₁₀ toC₃₀ monoolefin represented by Structure I-1, a branched C₁₀ to C₃₀monoolefin represented by Structure J-1, a branched C₁₀ to C₃₀monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof.

In yet other aspects, a C₂₀₊ sulfides composition can comprise at leastabout 10 wt. %, alternatively at least about 15 wt. %, alternatively atleast about 20 wt. %, or alternatively at least about 25 wt. % sulfides;wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at leastabout 85 wt. % of the sulfides can be branched C₂₀ to C₆₀ sulfidesrepresented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ can eachindependently be a functional group derived from an olefin, and whereinthe olefin comprises a branched C₁₀ to C₃₀ monoolefin, alternatively abranched C₁₁ to C₃₀ monoolefin, alternatively a branched C₁₂ to C₃₀monoolefin, alternatively a branched C₁₄ to C₃₀ monoolefin,alternatively a branched C₁₆ to C₂₈ monoolefin, or alternatively abranched C₁₈ to C₂₆ monoolefin. In such aspects, the olefin can comprisea branched C₁₀ to C₃₀ monoolefin represented by Structure I-1, abranched C₁₀ to C₃₀ monoolefin represented by Structure J-1, a branchedC₁₀ to C₃₀ monoolefin represented by Structure K-1, a branched C₁₀ toC₃₀ monoolefin represented by Structure L-1, or combinations thereof.

In still yet other aspects, a C₂₀₊ sulfides composition can comprisefrom at least about 10 wt. % to at least about 30 wt. %, alternativelyfrom at least about 12.5 wt. % to at least about 22.5 wt. %, oralternatively from at least about 15 wt. % to at least about 20 wt. %sulfides; wherein at least about 50 wt. %, alternatively at least about60 wt. %, alternatively at least about 70 wt. %, alternatively at leastabout 75 wt. %, alternatively at least about 80 wt. %, or alternativelyat least about 85 wt. % of the sulfides can be branched C₂₀ to C₆₀sulfides represented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹can each independently be a functional group derived from an olefin, andwherein the olefin comprises a branched C₁₀ to C₃₀ monoolefin,alternatively a branched C₁₁ to C₃₀ monoolefin, alternatively a branchedC₁₂ to C₃₀ monoolefin, alternatively a branched C₁₄ to C₃₀ monoolefin,alternatively a branched C₁₆ to C₂₈ monoolefin, or alternatively abranched C₁₈ to C₂₆ monoolefin. In such aspects, the olefin can comprisea branched C₁₀ to C₃₀ monoolefin represented by Structure I-1, abranched C₁₀ to C₃₀ monoolefin represented by Structure J-1, a branchedC₁₀ to C₃₀ monoolefin represented by Structure K-1, a branched C₁₀ toC₃₀ monoolefin represented by Structure L-1, or combinations thereof.

In still yet other aspects, a C₂₀₊ sulfides composition can consist ofor consist essentially of branched C₂₀ to C₆₀ sulfides represented bystructure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ can each independently bea functional group derived from an olefin, and wherein the olefincomprises a branched C₁₀ to C₃₀ monoolefin, alternatively a branched C₁₁to C₃₀ monoolefin, alternatively a branched C₁₂ to C₃₀ monoolefin,alternatively a branched C₁₄ to C₃₀ monoolefin, alternatively a branchedC₁₆ to C₂₈ monoolefin, or alternatively a branched C₁₈ to C₂₆monoolefin. In such aspects, the olefin can comprise a branched C₁₀ toC₃₀ monoolefin represented by Structure I-1, a branched C₁₀ to C₃₀monoolefin represented by Structure J-1, a branched C₁₀ to C₃₀monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof.

In still yet other aspects, a C₂₀₊ sulfides composition can comprise atleast about 5 wt. %, alternatively at least about 10 wt. %,alternatively at least about 15 wt. %, or alternatively at least about20 wt. % branched C₂₀ to C₆₀ sulfides represented by structureR¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ can each independently be afunctional group derived from an olefin, and wherein the olefincomprises a branched C₁₀ to C₃₀ monoolefin, alternatively a branched C₁₁to C₃₀ monoolefin, alternatively a branched C₁₂ to C₃₀ monoolefin,alternatively a branched C₁₄ to C₃₀ monoolefin, alternatively a branchedC₁₆ to C₂₈ monoolefin, or alternatively a branched C₁₈ to C₂₆monoolefin. In such aspects, the olefin can comprise a branched C₁₀ toC₃₀ monoolefin represented by Structure I-1, a branched C₁₀ to C₃₀monoolefin represented by Structure J-1, a branched C₁₀ to C₃₀monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof.

In still yet other aspects, a C₂₀₊ sulfides composition comprises atleast about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,75, 80, 85, 90, 95, or 99 wt. % branched C₂₀ to C₆₀ sulfides representedby structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹ can each independentlybe a functional group derived from an olefin, and wherein the olefincomprises a branched C₁₀ to C₃₀ monoolefin, alternatively a branched C₁₁to C₃₀ monoolefin, alternatively a branched C₁₂ to C₃₀ monoolefin,alternatively a branched C₁₄ to C₃₀ monoolefin, alternatively a branchedC₁₆ to C₂₈ monoolefin, or alternatively a branched C₁₈ to C₂₆monoolefin. In such aspects, the olefin can comprise a branched C₁₀ toC₃₀ monoolefin represented by Structure I-1, a branched C₁₀ to C₃₀monoolefin represented by Structure J-1, a branched C₁₀ to C₃₀monoolefin represented by Structure K-1, a branched C₁₀ to C₃₀monoolefin represented by Structure L-1, or combinations thereof.

In an aspect, a C₁₀₊ mercaptans/C₂₀₊ sulfides composition can compriseone or more mercaptans and one or more sulfides of the type disclosedherein. For purposes of the disclosure herein, a composition comprising(i) mercaptans, wherein at least a portion of the mercaptans arebranched C₁₀ to C₃₀ mercaptans, and (ii) sulfides, wherein at least aportion of the sulfides are branched C₂₀ to C₆₀ sulfides, can also bereferred to as a “branched C₁₀₊ mercaptans/branched C₂₀₊ sulfidescomposition.” In an aspect, the C₁₀₊ mercaptans/C₂₀₊ sulfidescomposition can comprise any suitable amount of branched C₁₀ to C₃₀mercaptans, and any suitable amount of branched C₂₀ to C₆₀ sulfides.

In an aspect, a C₁₀₊ mercaptans/C₂₀₊ sulfides composition can comprise(A) at least about 1 wt. %, alternatively at least about 5 wt. %,alternatively at least about 10 wt. %, alternatively at least about 15wt. %, alternatively at least about 20 wt. %, alternatively at leastabout 25 wt. %, alternatively at least about 30 wt. %, alternatively atleast about 40 wt. %, alternatively at least about 50 wt. %,alternatively at least about 60 wt. %, alternatively at least about 70wt. %, alternatively at least about 80 wt. %, alternatively at leastabout 90 wt. %, alternatively at least about 95 wt. %, or alternativelyat least about 99 wt. % mercaptans, wherein at least a portion of themercaptans can be branched C₁₀ to C₃₀ mercaptans characterized by thegeneral formula R¹⁴—SH, wherein R¹⁴ is a branched alkyl group; andwherein R¹⁴ has from 10 to 30 carbon atoms, alternatively from 11 to 30carbon atoms, alternatively from 12 to 30 carbon atoms, alternativelyfrom 14 to 30 carbon atoms, alternatively from 16 to 28 carbon atoms, oralternatively from 18 to 26 carbon atoms; and (B) at least about 1 wt.%, alternatively at least about 5 wt. %, alternatively at least about 10wt. %, alternatively at least about 20 wt. %, alternatively at leastabout 30 wt. %, alternatively at least about 40 wt. %, alternatively atleast about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 80wt. %, alternatively at least about 90 wt. %, alternatively at leastabout 95 wt. %, or alternatively at least about 99 wt. % sulfides,wherein at least a portion of the sulfides can be branched C₂₀ to C₆₀sulfides represented by structure R¹⁰—S—R¹¹, wherein both R¹⁰ and R¹¹can each independently be a functional group derived from an olefin, andwherein the olefin comprises a branched C₁₀ to C₃₀ monoolefin,alternatively a branched C₁₁ to C₃₀ monoolefin, alternatively a branchedC₁₂ to C₃₀ monoolefin, alternatively a branched C₁₄ to C₃₀ monoolefin,alternatively a branched C₁₆ to C₂₈ monoolefin, or alternatively abranched C₁₈ to C₂₆ monoolefin. In such aspect, the branched C₁₀ to C₃₀mercaptans characterized by the general formula R¹⁴—SH can be selectedfrom the group consisting of a branched C₁₀ to C₃₀ mercaptan representedby Structure A-1, a branched C₁₀ to C₃₀ mercaptan represented byStructure B-1, a branched C₁₀ to C₃₀ mercaptan represented by StructureC-1, a branched C₁₀ to C₃₀ mercaptan represented by Structure D-1, abranched C₁₀ to C₃₀ mercaptan represented by Structure E-1, a branchedC₁₀ to C₃₀ mercaptan represented by Structure F-1, a branched C₁₀ to C₃₀mercaptan represented by Structure G-1, a branched C₁₀ to C₃₀ mercaptanrepresented by Structure H-1, and combinations thereof; and the olefincan comprise a branched C₁₀ to C₃₀ monoolefin represented by StructureI-1, a branched C₁₀ to C₃₀ monoolefin represented by Structure J-1, abranched C₁₀ to C₃₀ monoolefin represented by Structure K-1, a branchedC₁₀ to C₃₀ monoolefin represented by Structure L-1, or combinationsthereof.

In an aspect, a C₁₀₊ mercaptans/C₂₀₊ sulfides composition can compriseC₁₀ to C₃₀ mercaptans characterized by the general formula R¹⁴—SH and/orC₂₀ to C₆₀ sulfides represented by structure R¹⁰—S—R¹¹ that are formedby reacting an olefin feedstock comprising olefins with H₂S as describedin more detail herein, wherein the olefins present in the olefinfeedstock provide the alkyl group represented by R¹⁰, R¹¹, and R¹⁴. Insuch aspects, the R¹⁰ and R¹¹ groups of the C₂₀ to C₆₀ sulfides and/orthe R¹⁴ group of the C₁₀ to C₃₀ mercaptans are provided by or derivedfrom the counterpart R¹⁰, R¹¹, and R¹⁴ groups present in the olefins inthe olefin feedstock. In an aspect, R¹⁰, R¹¹, and R¹⁴ can eachindependently be an alkyl group, wherein at least a portion of the alkylgroups can comprise a functional group derived from an olefin, whereinthe olefin is present in a feedstock as disclosed herein (e.g., a firstC₁₀ to C₃₀ feedstock; a second C₁₀ to C₃₀ feedstock).

In an aspect, a C₁₀₊ mercaptans composition and/or a C₁₀₊mercaptans/C₂₀₊ sulfides composition comprising equal to or greater thanabout 25 wt. % C₁₀₊ branched mercaptans as disclosed herein canadvantageously have an odor less unpleasant and less offensive than anodor of an otherwise similar composition comprising equal to or greaterthan about 25 wt. % n-decyl mercaptan, as perceived by equal to orgreater than about 51% of human subjects exposed to the odor of eachcomposition.

In an aspect, a C₁₀₊ mercaptans composition and/or a C₁₀₊mercaptans/C₂₀₊ sulfides composition comprising equal to or greater thanabout 25 wt. % C₁₀₊ branched mercaptans as disclosed herein canadvantageously have an odor less unpleasant than an odor of an otherwisesimilar composition comprising equal to or greater than about 25 wt. %n-dodecyl mercaptan and/or tert-dodecyl mercaptan, as perceived by equalto or greater than about 51% of human subjects exposed to the odor ofeach composition. Additional advantages of the C₁₀₊ mercaptanscompositions, C₂₀₊ sulfides compositions, and C₁₀₊ mercaptans/C₂₀₊sulfides compositions and processes of producing same as disclosedherein can be apparent to one of skill in the art viewing thisdisclosure.

In an aspect, a process of the present disclosure comprises reactingbranched C₁₀₊ mercaptans and a sulfur-containing material to produce aC₂₀₊ crude product. In a further aspect, a process of the presentdisclosure comprises reacting a feedstock comprising one or morebranched C₁₀₊ mercaptans and a sulfur-containing material in thepresence of a catalyst to produce a C₂₀₊ crude product; wherein the C₂₀₊crude product comprises branched C₂₀₊ polysulfides and branched C₂₀₊monosulfides.

In an aspect, a process of the present disclosure comprises reactingfeedstock comprising one or more branched C₁₀₊ mercaptans and asulfur-containing material (e.g., elemental sulfur) in the presence of acatalyst to produce a branched C₂₀₊ polysulfides crude product; whereinthe branched C₁₀₊ mercaptans comprise C₁₀ to C₃₀ mercaptans,alternatively C₁₁ to C₃₀ mercaptans, alternatively C₁₂ to C₃₀mercaptans, alternatively C₁₄ to C₃₀ mercaptans, alternatively C₁₆ toC₂₈ mercaptans, or alternatively C₁₈ to C₂₆ mercaptans; and wherein thebranched C₂₀₊ polysulfides crude product comprises branched C₂₀₊polysulfides and branched C₂₀₊ monosulfides. In a further aspect, thebranched C₁₀₊ mercaptans are derived from one or more branched C₁₀₊monoolefins wherein the branched C₁₀₊ monoolefins are produced byreacting, in a reactor, a sulfur source (e.g., H₂S) and a feedstockcomprising the branched C₁₀₊ monoolefins in the presence of aninitiating agent, as previously described herein.

The branched C₂₀₊ polysulfides crude product can be further processed,for example via distillation, as previously described herein for thebranched C₁₀₊ mercaptans, to yield one or more products (also referredto as distilled, purified, refined, finished, or final products)selected from the group consisting of C₂₀₊ polysulfide compositions(e.g., a composition comprising one or more branched C₂₀₊ polysulfides);C₂₀₊ monosulfide compositions (e.g., a composition comprising one ormore branched C₂₀₊ monosulfides); and compositions having both branchedC₂₀₊ polysulfides and branched C₂₀₊ monosulfides, referred to as C₂₀₊metasulfide compositions.

In an aspect, a C₂₀₊ polysulfides composition comprises one or morebranched C₂₀₊ polysulfides represented by the general formulaR¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integer from 1 to 10, and whereinR¹⁵S¹ and R¹⁶S² are each independently a functional group derived from amercaptan, wherein the mercaptan comprises a branched C₁₀₊ mercaptan asdisclosed herein. The branched C₂₀₊ polysulfides may comprise C₂₀ to C₆₀polysulfides, alternatively C₂₁ to C₆₀ polysulfides, alternatively C₂₂to C₆₀ polysulfides, alternatively C₂₄ to C₆₀ polysulfides,alternatively C₂₈ to C₆₀ polysulfides, alternatively C₃₂ to C₅₆polysulfides, or alternatively C₃₆ to C₅₂ polysulfides.

In an aspect, a C₂₀₊ monosulfides composition comprises one or morebranched C₂₀₊ monosulfides represented by the general formula R¹⁷—S—R¹⁸,wherein R¹⁷ and R¹⁸ are each independently an alkyl group, wherein thealkyl group comprises a branched C₁₀₊ alkyl group as disclosed herein.The branched C₂₀₊ monosulfides comprise C₂₀ to C₆₀ monosulfides,alternatively C₂₁ to C₆₀ monosulfides, alternatively C₂₂ to C₆₀monosulfides, alternatively C₂₄ to C₆₀ monosulfides, alternatively C₂₈to C₆₀ monosulfides, alternatively C₃₂ to C₅₆ monosulfides, oralternatively C₃₆ to C₅₂ monosulfides.

In an aspect, a C₂₀₊ metasulfides composition (e.g., a C₂₀₊polysulfides/C₂₀₊ monosulfides composition) comprises (A) one or morebranched C₂₀₊ polysulfides represented by the general formulaR¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integer from 1 to 10; and (B) oneor more branched C₂₀₊ monosulfides represented by the general formulaR¹⁷—S—R¹⁸.

The C₂₀₊ polysulfide compositions, the C₂₀₊ monosulfides compositions,and the C₂₀₊ metasulfides compositions can be salable or otherwise usedfor a variety of end uses such as mining ore collector compositions andchain transfer agents.

In an aspect, the compositions disclosed herein can be prepared by aprocess comprising reacting branched C₁₀₊ mercaptans and asulfur-containing material to produce a branched C₂₀₊ polysulfides crudeproduct, wherein the branched C₁₀₊ mercaptans may comprise a branchedC₁₀₊ mercaptan represented by Structure A-1, Structure B-1, StructureC-1, Structure D-1, Structure E-1, Structure F-1, Structure G-1,Structure H-1, or combinations thereof; wherein R⁹ is a C₁ to C₂₁ alkylgroup, alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁alkyl group, alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇to C₁₉ alkyl group, or alternatively a C₉ to C₁₇ alkyl group. The R⁹group can be a linear C₁ to C₂₁ alkyl group or a branched C₁ to C₂₁alkyl group. As will be appreciated by one of skill in the art, and withthe help of this disclosure, the branched C₁₀₊ mercaptans comprising theR⁹ alkyl group are branched mercaptans, regardless of whether R⁹ islinear or branched, owing to a branched sub-structure that is linked tothe R⁹ alkyl group, as it can be seen in Structure A-1, Structure B-1,Structure C-1, Structure D-1, Structure E-1, Structure F-1, StructureG-1, and Structure H-1, as previously disclosed herein.

In some aspects, R⁹ can be selected from the group consisting of amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, adecyl group, an undecyl group, a dodecyl group, a tridecyl group, atetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecylgroup, an octadecyl group, a nonadecyl group, an eicosyl group, ahenicosyl group, and combinations thereof.

In aspects where R⁹ is a methyl group, the branched C₁₀₊ mercaptanscomprise one or more branched C₁₀ mercaptans, as previously disclosedherein. In an aspect, the branched C₁₀ mercaptans may comprise5-methyl-1-mercapto-nonane (represented by Structure A),3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), or combinationsthereof.

Any feedstock comprising one or more branched C₁₀₊ mercaptans of thetype described herein can be used, for example a reaction product of theprocess of reacting H₂S and one or more branched C₁₀₊ monoolefins(alternatively, one or more branched C₁₀ monoolefins), in the presenceof an initiating agent as previously described herein. In an aspect, afeedstock of branched C₁₀₊ mercaptans may comprise any mercaptancomposition previously described herein such as a “C₁₀₊ mercaptanscomposition”, a “C₁₁₊ mercaptans composition”, a “mercaptan composition”(also referred to as a “branched C₁₀ mercaptan composition”), orcombinations thereof. In a further aspect, the feedstock of branchedC₁₀₊ mercaptans may comprise any mercaptan/sulfide compositionpreviously described herein such as a “C₁₀₊ mercaptans/C₂₀₊ sulfidescomposition”, a “C₁₁₊ mercaptans/C₂₂₊ sulfides composition”, a“mercaptan/sulfide composition” (also referred to as a “branched C₁₀mercaptan/C₂₀ sulfide composition”), or combinations thereof. Suchfeedstocks can comprise other mercaptans in addition to the branchedC₁₀₊ mercaptans of the type described herein, for example linear C₁₀₊mercaptans as well as mercaptans having less than 10 carbon atoms.

In an aspect, the feedstock can comprise one or more branched C₁₀ to C₃₀mercaptans. Any feedstock comprising branched C₁₀ to C₃₀ mercaptans ofthe type described herein can be used, for example a reaction product ofthe process of reacting H₂S and one or more branched C₁₀₊ monoolefins inthe presence of an initiating agent as described herein. Such feedstockscan comprise other mercaptans in addition to the branched C₁₀ to C₃₀mercaptans of the type described herein, for example C⁹⁻ mercaptans,C₃₁₊ mercaptans, as well as linear C₁₀ to C₃₀ mercaptans.

In an aspect, the feedstock can comprise at least about 70 wt. %,alternatively at least about 75 wt. %, alternatively at least about 80wt. %, alternatively at least about 85 wt. %, alternatively at leastabout 90 wt. %, or alternatively at least about 95 wt. % branched C₁₀ toC₃₀ mercaptans, based on the total weight of the feedstock. In suchaspect, the feedstock can comprise (a) less than about 15 wt. %,alternatively less than about 10 wt. %, alternatively less than about 5wt. %, or alternatively less than about 1 wt. % C⁹⁻ mercaptans; and (b)less than about 15 wt. %, alternatively less than about 10 wt. %,alternatively less than about 5 wt. %, or alternatively less than about1 wt. % C₃₁₊ mercaptans; based on the total weight of the feedstock. Forpurposes of the disclosure herein, a feedstock comprising at least about70 wt. % branched C₁₀ to C₃₀ mercaptans, based on the total weight ofthe feedstock, can also be referred to as a “first C₁₀ to C₃₀ mercaptansfeedstock.”

In another aspect, the feedstock can comprise at least about 95 wt. %,alternatively at least about 96 wt. %, alternatively at least about 97wt. %, alternatively at least about 98 wt. %, or alternatively at leastabout 99 wt. % branched C₁₀ to C₃₀ mercaptans, based on the total weightof the feedstock. For purposes of the disclosure herein, a feedstockcomprising at least about 95 wt. % branched C₁₀ to C₃₀ mercaptans, basedon the total weight of the feedstock, can also be referred to as a“second C₁₀ to C₃₀ mercaptans feedstock.” In an aspect, the second C₁₀to C₃₀ mercaptans feedstock can be produced by purifying the first C₁₀to C₃₀ mercaptans feedstock, such as for example by distillation of thefirst C₁₀ to C₃₀ mercaptans feedstock.

In an aspect, the branched C₁₀ to C₃₀ mercaptans of any feedstockdescribed herein (e.g., a first C₁₀ to C₃₀ mercaptans feedstock or asecond C₁₀ to C₃₀ mercaptans feedstock) can comprise, can consistessentially of, or can be, a branched C₁₀₊ mercaptan represented byStructure A-1, Structure B-1, Structure C-1, Structure D-1, StructureE-1, Structure F-1, Structure G-1, Structure H-1, wherein R⁹ is a C₁ toC₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group, alternatively aC₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkyl group,alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ to C₁₇alkyl group.

In an aspect, the C₁₀ to C₃₀ mercaptans of any feedstock describedherein (e.g., a first C₁₀ to C₃₀ mercaptans feedstock or a second C₁₀ toC₃₀ mercaptans feedstock) can further comprise non-branched C₁₀₊mercaptans, such as for example a linear C₁₀ to C₃₀ mercaptanrepresented by Structure M-1, Structure N-1, Structure O-1, StructureP-1, or combinations thereof, wherein R⁹ is a C₁ to C₂₁ alkyl group,alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁ alkylgroup, alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉alkyl group, or alternatively a C₉ to C₁₇ alkyl group.

In aspects where R⁹ is a methyl group, the non-branched C₁₀₊ mercaptanscan further comprise non-branched C₁₀ mercaptans, as previouslydisclosed herein. The non-branched C₁₀ mercaptans can comprise1-mercapto-decane (represented by Structure M), 4-mercapto-decane(represented by Structure N), 5-mercapto-decane (represented byStructure O), 2-mercapto-decane (represented by Structure P), orcombinations thereof.

In an aspect, the C₁₀ to C₃₀ mercaptans of any feedstock describedherein (e.g., a first C₁₀ to C₃₀ feedstock or a second C₁₀ to C₃₀feedstock) can comprise linear C₁₀ to C₃₀ mercaptans. In an aspect, theC₁₀ to C₃₀ mercaptans of any feedstock described herein can compriseless than or equal to about 26 mol %, alternatively less than or equalto about 24 mol %, alternatively less than or equal to about 22 mol %,alternatively less than or equal to about 20 mol %, or alternativelyless than or equal to about 18 mol % linear C₁₀ to C₃₀ mercaptans. Insome aspects, the C₁₀ to C₃₀ mercaptans of any feedstock describedherein can comprise from about 0.1 mol % to about 26 mol %,alternatively from about 0.5 mol % to about 24 mol %, alternatively fromabout 1 mol % to about 22 mol %, alternatively from about 1.5 mol % toabout 20 mol %, or alternatively from about 2.5 mol % to about 18 mol %linear C₁₀ to C₃₀ mercaptans.

In an aspect, the first C₁₀ to C₃₀ mercaptans feedstock disclosed hereincan further comprise C⁹⁻ mercaptans, C₃₁₊ mercaptans, or combinationsthereof; alternatively, C⁹⁻ mercaptans; or alternatively, C₃₁₊mercaptans. In an aspect, the C⁹⁻ mercaptans can comprise, can consistessentially of, or can be, C₇ mercaptans, C₈ mercaptans, C₉ mercaptans,or combinations thereof; alternatively, C₇ mercaptans; alternatively, C₈mercaptans; or alternatively, C₉ mercaptans. In some aspects, the C⁹⁻mercaptans can comprise, can consist essentially of, or can be, C₈mercaptans. In an aspect, the C₃₁₊ mercaptans can comprise, can consistessentially of, or can be, C₃₁ mercaptans, C₃₂ mercaptans, C₃₃mercaptans, C₃₄ mercaptans, C₃₅ mercaptans, C₃₆ mercaptans, C₃₇mercaptans, C₃₈ mercaptans, or combinations thereof; alternatively, C₃₁mercaptans; alternatively, C₃₂ mercaptans; alternatively, C₃₃mercaptans; alternatively, C₃₄ mercaptans; alternatively, C₃₅mercaptans; alternatively, C₃₆ mercaptans; alternatively, C₃₇mercaptans; or alternatively, C₃₈ mercaptans. In some aspects, the C₃₁₊mercaptans can comprise, can consist essentially of, or can be, C₃₂mercaptans, C₃₆ mercaptans, C₃₈ mercaptans, or combinations thereof;alternatively, C₃₂ mercaptans; alternatively, C₃₆ mercaptans; oralternatively, C₃₈ mercaptans.

In an aspect, the first C₁₀ to C₃₀ mercaptans feedstock can furthercomprise from about 0.1 mol % to about 5 mol %, alternatively from about0.25 mol % to about 4 mol %, or alternatively from about 0.5 mol % toabout 3 mol % C₈ mercaptans. In such aspect, the C₈ mercaptans cancomprise at least about 95 mol %, alternatively at least about 96 mol %,alternatively at least about 97 mol %, alternatively at least about 98mol %, or alternatively at least about 99 mol % 1-octanethiol.

In an aspect, a feedstock comprising branched C₁₀₊ mercaptans and asulfur-containing material can be reacted in the presence of a catalystto produce a branched C₂₀₊ polysulfides crude product wherein thesulfur-containing material comprises any sulfur-containing materialsuitable to provide sulfur for the conversion of mercaptans topolysulfides. In a particular aspect, the sulfur-containing materialcomprises elemental sulfur. In a further aspect, elemental sulfursuitable for use herein comprises one or more allotropes of elementalsulfur, e.g., cyclo-S₈ or amorphous sulfur. The sulfur-containingmaterial may further comprise one or more polymorphs of elementalsulfur, e.g., α-sulfur (α-cyclo-S₈) or β-sulfur (β-cyclo-S₈). In a stillfurther aspect, the sulfur-containing material does not comprisehydrogen sulfide (H₂S).

In an aspect, an equivalent molar ratio of sulfur-containing material tomercaptans is in a range of from about 0.01:1 to about 20:1,alternatively from about 0.04:1 to about 10:1, alternatively from about0.07:1 to about 1.2:1, or alternatively, from about 0.4:1 to about0.8:1.

In an aspect, a feedstock comprising branched C₁₀₊ mercaptans and asulfur-containing material can be reacted in the presence of a catalystto produce a branched C₂₀₊ polysulfides crude product wherein thecatalyst comprises a surfactant and an alkaline material.

In a further aspect, the surfactant may be any surfactant suitable forconversion of mercaptans to polysulfides as disclosed herein.Non-limiting examples of surfactants suitable for use in the presentdisclosure include nonionic surfactants, ionic surfactants, amphotericsurfactants, or combinations thereof. In an aspect, the surfactant maybe a nonionic surfactant. In a further aspect, the surfactant comprisesone or more functional groups including but not limited to alkoxylates,polyalkoxylates, ethoxylates, polyethoxylates, glucosides, sulfates,sulfonates, disulfonates, phosphate esters, sulfosuccinates, quaternaryammonium salts, betaines, or combinations thereof. In yet a furtheraspect, the surfactant may be a nonionic surfactant comprising one ormore functional groups including polyalkoxylates, polyethoxylates, orglucosides; alternatively, polyalkoxylates; alternatively,polyethoxylates; or alternatively, glucosides. In a particular aspect,the surfactant may be a nonionic surfactant comprising a polyethoxylatedalcohol, a polyethoxylated mercaptan, or a combination thereof;alternatively, a polyethoxylated alcohol; or alternatively, apolyethoxylated mercaptan. The polyethoxylated alcohol may be anypolyethoxylated alcohol suitable for conversion of mercaptans topolysulfides. In a particular aspect, the polyethoxylated alcohol isrepresented by the formula C₁₀₋₁₈H₂₁₋₃₇O[C₂H₄O]_(x)H; whereinC₁₀₋₁₈H₂₁₋₃₇O is a functional group derived from a secondary alcoholcomprising from about 10 to about 18 carbons atoms; and wherein x is aninteger from 3 to 20, alternatively, from 4 to 10, or alternatively,from 6 to 8. In a further aspect, the polyethoxylated mercaptan may beany polyethoxylated mercaptan suitable for conversion of mercaptans topolysulfides. In an aspect, the polyethoxylated mercaptan is representedby the formula C₈₋₁₆H₁₇₋₃₃S[C₂H₄O]_(x)H; wherein C₈₋₁₆H₁₇₋₃₃S is afunctional group derived from a tertiary mercaptan comprising from about8 to about 16 carbons atoms; and wherein x is an integer from 3 to 20,alternatively, from 4 to 10, or alternatively, from 6 to 8.

In a still further aspect, the surfactant may be chosen from the groupconsisting of 1-Oleoyl-rac-glycerol, Brij® 58, Brij® L23, Brij® L4,Brij® 010, CYMAL-2®, CYMAL-5®, CYMAL-6®, Decaethylene glycol monododecylether, Decyl β-D-glucopyranoside, Decyl β-D-maltopyranoside,Deoxy-BigCHAP, Digitonin, ECOSURF™ EH-9, ECOSURF™ SA-9, Genapol® X-100,Igepal® CA-630, Igepal® CA-720, Kolliphor® P 188, Kolliphor® P 407,Kolliphor® EL, MEGA-8, MEGA-9, MEGA-10, Methoxypolyethylene glycol,N,N-Dimethyldodecylamine N-oxide, n-Dodecyl β-D-maltoside, n-Heptylβ-D-thioglucopyranoside, n-Hexadecyl β-D-maltoside,n-Nonyl-β-D-Glucopyranoside, n-Nonyl-β-D-maltoside,n-Octyl-β-D-maltoside, n-Octyl-β-D-thioglucopyranoside,n-Octyl-b-D-Glucopyranoside, Nonaethylene glycol monododecyl ether,Nonidet™ P40 Substitute, Nonylphenyl-polyethyleneglycol acetate,Octaethylene glycol monododecyl ether, Pluronic® F-127, Pluronic® F-68,Poloxamer 407, Poly(ethylene glycol), Polyoxyethylene (10) tridecylether, Polyoxyethylene (40) stearate, Polysorbate 20, Polysorbate 60,Polysorbate 80, Saponin, Span® 20, Span® 40, Span® 60, Span® 80, Span®85, Sucrose monolaurate, Synperonic® PE/P84, TERGITOL™, TERGITOL™ NP-7,TERGITOL™ NP-9, TERGITOL™ NP-10, TERGITOL™ NP-40, TERGITOL™ 15-S-7,TERGITOL™ 15-S-9, TERGITOL™ 15-S-30, TERGITOL™ 15-S-40, TERGITOL™ TMN 6,TERGITOL™ TMN 10, TERGITOL™ TMN-100X, Tetraethylene glycol monododecylether, Tetramethylammonium hydroxide pentahydrate, Thesit®, TRITON™X-100, TRITON™ X-114, TRITON™ X-165, TRITON™ X-305, TRITON™ X-405,TRITON™ X-405, TRITON™ X-705, TRITON™-CG-110, TWEEN® 20, TWEEN® 40,TWEEN® 60, TWEEN® 65, TWEEN® 80, TWEEN® 85, Tyloxapol, andUndecyl-β-D-maltoside, all of which are available commercially fromMilliporeSigma, and AQUA-CLEEN® available commercially from ChemicalProducts Industries, Inc. In a particular aspect the surfactant maycomprise TERGITOL® 15-S-7 or AQUA-CLEEN®.

In a further aspect, the alkaline material may comprise any alkalinematerial suitable for conversion of mercaptans to polysulfides asdisclosed herein. In a particular aspect, the alkaline material may be ametal hydroxide. In an aspect, the metal hydroxide may be a Group 1metal hydroxide, a Group 2 metal hydroxide, or a combination thereof. Inyet a further aspect, the metal hydroxide may be LiOH, NaOH, KOH, RbOH,CsOH, Mg(OH)₂, Ca(OH)₂, or combinations thereof. The metal hydroxidecomprising a catalyst suitable for use in the present disclosure may bea solid or, alternatively, may be a component of an aqueous solution. Inyet a further aspect, an amount of metal hydroxide comprising theaqueous solution may be about 5 wt. %; alternatively, about 10 wt. %;alternatively, about 20 wt. %; or alternatively, about 50 wt. % based onthe total weight of the aqueous solution.

In a particular aspect, prior to contacting the catalyst with any othercomponent of the reaction process, the surfactant and the alkalinematerial may be contacted and subsequently heated. In a further aspect,the surfactant and the alkaline material may be heated to a temperaturein a range of from about 40° C. to about 120° C., or alternatively, fromabout 60° C. to about 100° C. In yet a further aspect, the temperaturemay be maintained for a time period in a range of from 5 min to about 12h, or alternatively, from about 30 min to about 2 h.

In an aspect, a weight ratio of catalyst to mercaptans is in a range offrom about 0.001:1 to about 0.5:1, alternatively from about 0.002:1 toabout 0.05:1, alternatively from about 0.005:1 to about 0.013:1, oralternatively from about 0.006:1 to about 0.008:1.

In an aspect, a weight ratio of surfactant to alkaline material is in arange of from about 5:1 to about 500:1, alternatively from about 10:1 toabout 200:1, alternatively from about 25:1 to about 40:1, oralternatively from about 30:1 to about 35:1.

In an aspect, a feedstock comprising branched C₁₀₊ mercaptans and asulfur-containing material can be reacted in the presence of a catalystto produce a branched C₂₀₊ polysulfides crude product wherein amercaptan scavenger (i.e., quenching agent) may be utilized to producethe branched C₂₀₊ polysulfides crude product. In an aspect, themercaptan scavenger may be any mercaptan scavenger suitable forconversion of mercaptans to polysulfides. In a further aspect, themercaptan scavenger may be an epoxide, an oxetane, or a combinationthereof. In a further aspect, the epoxide may be ethylene oxide orpropylene oxide; alternatively, ethylene oxide; or alternatively,propylene oxide.

In an aspect, an equivalent molar ratio of mercaptan scavenger tomercaptans is in a range of from about 0.001:1 to about 1:1,alternatively from about 0.01:1 to about 0.5:1, alternatively from about0.05:1 to about 0.1:1, or alternatively from about 0.06:1 to about0.08:1.

In an aspect, a feedstock comprising branched C₁₀₊ mercaptans and asulfur-containing material can be reacted in the presence of a catalystto produce a branched C₂₀₊ polysulfides crude product wherein adecolorizing agent may be utilized to produce the branched C₂₀₊polysulfides crude product. In an aspect, the decolorizing agent may beany decolorizing agent suitable for use in the conversion of mercaptansto polysulfides. In a further aspect, the decolorizing agent comprisesactivated carbon, decolorizing carbon, mineral carbon, charcoal black,graphite (natural), purified charcoal, or a combination thereof. In afurther aspect, the decolorizing agent may comprise Darco G-60, Darco®,Norit A® and combinations thereof, available commercially fromSigma-Aldrich, Inc.

In an aspect, a weight ratio of decolorizing agent to mercaptans is in arange of from about 0.001:1 to about 0.2:1, alternatively from about0.01:1 to about 0.02:1, or alternatively from about 0.015:1 to about0.018:1.

Disclosed herein are processes of reacting a feedstock comprisingbranched C₁₀₊ mercaptans (e.g., a first C₁₀ to C₃₀ mercaptans feedstockor a second C₁₀ to C₃₀ mercaptans feedstock) and a sulfur-containingmaterial in the presence of a catalyst to produce a branched C₂₀₊polysulfides crude product. In an aspect, such a process may be referredto as a process of producing a C₂₀₊ polysulfides crude product. It willbe appreciated by the ordinary skilled artisan that the entirety of theprocesses (i.e., each process step), disclosed herein may be conductedunder an atmosphere comprising an inert gas. In a further aspect, theinert gas may comprise any inert gas suitable for use in the presentdisclosure, nonlimiting examples of which include nitrogen, argon, and acombination thereof.

Disclosed herein is a process of producing a C₂₀₊ polysulfides crudeproduct comprising contacting a feedstock comprising branched C₁₀₊mercaptans (e.g., a first C₁₀ to C₃₀ mercaptans feedstock or a secondC₁₀ to C₃₀ mercaptans feedstock) and a catalyst to form a mixture. In anaspect, the feedstock comprises one or more branched C₁₀ to C₃₀mercaptans as disclosed herein. The process further comprises heatingthe mixture to a temperature in a range of from about 40° C. to about200° C.; alternatively, from about 60° C. to about 85° C.; oralternatively, from about 70° C. to about 80° C. The mixture may then becontacted with a sulfur-containing material (e.g., elemental sulfur)wherein evolution of a reaction by-product occurs. In an aspect, thereaction by-product may be gas-phase hydrogen sulfide. The mixture maythen be agitated for a time period in a range of from 30 min to about 24h; alternatively, from about 1 h to about 12 h; alternatively, fromabout 2 h to about 6 h; or alternatively, from about 3 h to about 4 h.

In an aspect, the process of producing a C₂₀₊ polysulfides crude productcomprises raising the temperature of the mixture. The mixture may beheated to a temperature in a range of from about 40° C. to about 250°C.; alternatively, from about 60° C. to about 200° C.; alternatively,from about 90° C. to about 150° C.; or alternatively, from about 90° C.to about 100° C. The mixture may then be agitated for a time period in arange of from 30 min to about 24 h; alternatively, from about 1 h toabout 12 h; alternatively, from about 2 h to about 4 h; oralternatively, from about 3 h to about 4 h. The mixture may then besparged with an inert gas (e.g., nitrogen), for a time period in a rangeof from 5 min to about 24 h; alternatively, from about 10 min to about12 h; alternatively, from about 30 min to about 4 h; or alternatively,from about 1 h to about 4 h.

In a further aspect, the process of producing a C₂₀₊ polysulfides crudeproduct comprises lowering the temperature of the mixture. Thetemperature of the mixture may be adjusted to a temperature in a rangeof from about 50° C. to about 100° C.; alternatively, from about 65° C.to about 85° C.; or alternatively, from about 70° C. to about 75° C. Theprocess further comprises addition of a mercaptan scavenger (e.g.,propylene oxide), to the mixture. In an aspect, the mercaptan scavenger(e.g., propylene oxide), may be added to the mixture over a time periodin a range of from about 1 min to about 10 h; alternatively, from about5 min to about 6 h; or alternatively, from about 10 min to about 2 h.The mixture may then be agitated for a time period in a range of from 10min to about 24 h; alternatively, from about 30 min to about 12 h;alternatively, from about 1 h to about 4 h; or alternatively, from about2 h to about 3 h. The mixture may then be sparged with an inert gas(e.g., nitrogen), for a time period in a range of from 5 min to about 24h; alternatively, from about 10 min to about 12 h; alternatively, fromabout 30 min to about 4 h; or alternatively, from about 1 h to about 4h.

In a particular aspect, the process of producing a C₂₀₊ polysulfidescrude product comprises collecting a C₂₀₊ polysulfides crude product.The C₂₀₊ polysulfides crude product may be collected by any suitableliquid/solid separation technique known to the ordinary skilled artisan.Non-limiting examples of techniques for collecting the C₂₀₊ polysulfidescrude product include filtration (e.g., gravity, in-line, membrane,pressure, vacuum), centrifugation, gravimetric settling, hydrocyclonemethods, sedimentation, or combinations thereof. In an aspect,subsequent to sparging the mixture with the inert gas, the mixture maybe cooled to a temperature in a range of from about 15° C. to about 50°C., or alternatively, from about 20° C. to about 35° C. to form a cooledmixture. In a further aspect, the cooled mixture may be filtered tocollect the C₂₀₊ polysulfides crude product. Alternatively, prior tocollecting the C₂₀₊ polysulfides crude product, activated carbon of thetype disclosed herein is added to the cooled mixture and the temperatureof the cooled mixture is raised to a temperature in a range of fromabout 40° C. to about 80° C.; or alternatively, from about 50° C. toabout 70° C. The mixture is then agitated for a time period in a rangeof from 10 min to about 12 h; alternatively, from about 1 h to about 4h; or alternatively, from about 2 h to about 3 h. The process furthercomprises cooling the mixture to a temperature in a range of from about15° C. to about 50° C., or alternatively, from about 20° C. to about 35°C. and collecting (e.g., filtering), the C₂₀₊ polysulfides crudeproduct.

Disclosed herein is a process of producing a C₂₀₊ polysulfides crudeproduct comprising contacting a feedstock comprising branched C₁₀₊mercaptans (e.g., a first C₁₀ to C₃₀ mercaptans feedstock or a secondC₁₀ to C₃₀ mercaptans feedstock), a catalyst and a sulfur-containingmaterial to form a mixture. In an aspect the sulfur-containing materialcomprises elemental sulfur and the feedstock comprises one or morebranched C₁₀ to C₃₀ mercaptans as disclosed herein. The process furthercomprises heating the mixture to a temperature in a range of from about40° C. to about 200° C.; alternatively, from about 60° C. to about 85°C.; or alternatively, from about 70° C. to about 80° C. whereinevolution of a reaction by-product occurs. In an aspect, the reactionby-product may be gas-phase hydrogen sulfide. The mixture may then beagitated for a time period in a range of from 30 min to about 24 h;alternatively, from about 1 h to about 12 h; alternatively, from about 2h to about 6 h; or alternatively, from about 3 h to about 4 h.

In an aspect, the process of producing a C₂₀₊ polysulfides crude productcomprises raising the temperature of the mixture. The mixture may beheated to a temperature in a range of from about 40° C. to about 250°C.; alternatively, from about 60° C. to about 200° C.; alternatively,from about 90° C. to about 150° C.; or alternatively, from about 90° C.to about 100° C. The mixture may then be agitated for a time period in arange of from 30 min to about 24 h; alternatively, from about 1 h toabout 12 h; alternatively, from about 2 h to about 4 h; oralternatively, from about 3 h to about 4 h. The mixture may then besparged with an inert gas (e.g., nitrogen), for a time period in a rangeof from 5 min to about 24 h; alternatively, from about 10 min to about12 h; alternatively, from about 30 min to about 4 h; or alternatively,from about 1 h to about 4 h.

In a further aspect, the process of producing a C₂₀₊ polysulfides crudeproduct comprises lowering the temperature of the mixture. Thetemperature of the mixture may be adjusted to a temperature in a rangeof from about 50° C. to about 100° C.; alternatively, from about 65° C.to about 85° C.; or alternatively, from about 70° C. to about 75° C. Theprocess further comprises addition of a mercaptan scavenger (e.g.,propylene oxide), to the mixture. In an aspect, the mercaptan scavenger(e.g., propylene oxide), may be added to the mixture over a time periodin a range of from about 1 min to about 10 h; alternatively, from about5 min to about 6 h; or alternatively, from about 10 min to about 2 h.The mixture may then be agitated for a time period in a range of from 10min to about 24 h; alternatively, from about 30 min to about 12 h;alternatively, from about 1 h to about 4 h; or alternatively, from about2 h to about 3 h. The mixture may then be sparged with an inert gas(e.g., nitrogen), for a time period in a range of from 5 min to about 24h; alternatively, from about 10 min to about 12 h; alternatively, fromabout 30 min to about 4 h; or alternatively, from about 1 h to about 4h.

In a particular aspect, the process of producing a C₂₀₊ polysulfidescrude product comprises collecting a C₂₀₊ polysulfides crude product.The C₂₀₊ polysulfides crude product may be collected by any suitableliquid/solid separation technique known to the ordinary skilled artisan.Non-limiting examples of techniques for collecting the C₂₀₊ polysulfidescrude product include filtration (e.g., gravity, in-line, membrane,pressure, vacuum), centrifugation, gravimetric settling, hydrocyclonemethods, sedimentation, or combinations thereof. In an aspect,subsequent to sparging the mixture with the inert gas, the mixture maybe cooled to a temperature in a range of from about 15° C. to about 50°C., or alternatively, from about 20° C. to about 35° C. to form a cooledmixture. In a further aspect, the cooled mixture may be filtered tocollect the C₂₀₊ polysulfides crude product. Alternatively, prior tocollecting the C₂₀₊ polysulfides crude product, activated carbon of thetype disclosed herein is added to the cooled mixture and the temperatureof the cooled mixture is raised to a temperature in a range of fromabout 40° C. to about 80° C.; or alternatively, from about 50° C. toabout 70° C. The mixture is then agitated for a time period in a rangeof from 10 min to about 12 h; alternatively, from about 1 h to about 4h; or alternatively, from about 2 h to about 3 h. The process furthercomprises cooling the mixture to a temperature in a range of from about15° C. to about 50° C., or alternatively, from about 20° C. to about 35°C. and collecting (e.g., filtering), the C₂₀₊ polysulfides crudeproduct.

In a particular aspect of the present disclosure, a process of producinga C₂₀₊ polysulfides crude product comprises reacting, in a reactor, asulfur source (e.g., H₂S) and a feedstock comprising one or morebranched C₁₀₊ monoolefins in the presence of an initiating agent, toproduce a branched C₁₀₊ mercaptans crude composition, i.e., the processpreviously described herein for the branched C₁₀₊ monoolefins. Theprocess further comprises recovering an intermediate reaction productfrom the branched C₁₀₊ mercaptans crude composition. In an aspect, theintermediate reaction product recovered from the branched C₁₀₊mercaptans crude composition may be a branched C₁₀₊ mercaptanscomposition, a branched C₁₀₊ mercaptans/branched C₂₀₊ sulfidescomposition, or a combination thereof as previously described herein forthe reaction of the branched C₁₀₊ monoolefins. In a further aspect, theintermediate reaction product comprises one or more branched C₁₀ to C₃₀mercaptans as previously described herein. In yet a further aspect, theintermediate reaction product may be recovered from the branched C₁₀₊mercaptans crude composition, for example by flashing, distillation,fractionation, stripping, absorption, etc. as previously describedherein.

In an aspect, the process of producing a C₂₀₊ polysulfides crude productcomprises contacting the intermediate reaction product and a catalyst toform a mixture. The process further comprises heating the mixture to atemperature in a range of from about 40° C. to about 200° C.;alternatively, from about 60° C. to about 85° C.; or alternatively, fromabout 70° C. to about 80° C. The mixture may then be contacted with asulfur-containing material (e.g., elemental sulfur) wherein evolution ofa reaction by-product occurs. In an aspect, the reaction by-product maybe gas-phase hydrogen sulfide. The mixture may then be agitated for atime period in a range of from 30 min to about 24 h; alternatively, fromabout 1 h to about 12 h; alternatively, from about 2 h to about 6 h; oralternatively, from about 3 h to about 4 h. In a further aspect, themixture may be heated to a temperature in a range of from about 40° C.to about 250° C.; alternatively, from about 60° C. to about 200° C.;alternatively, from about 90° C. to about 150° C.; or alternatively,from about 90° C. to about 100° C. The mixture may then may be agitatedfor a time period in a range of from 30 min to about 24 h;alternatively, from about 1 h to about 12 h; alternatively, from about 2h to about 4 h; or alternatively, from about 3 h to about 4 h. Themixture may then be sparged with an inert gas (e.g., nitrogen), for atime period in a range of from 5 min to about 24 h; alternatively, fromabout 10 min to about 12 h; alternatively, from about 30 min to about 4h; or alternatively, from about 1 h to about 4 h. In a further aspect,the mixture may be cooled to a temperature in a range of from about 50°C. to about 100° C.; alternatively, from about 65° C. to about 85° C.;or alternatively, from about 70° C. to about 75° C. The process furthercomprises addition of a mercaptan scavenger (e.g., propylene oxide), tothe mixture. In an aspect, the mercaptan scavenger (e.g., propyleneoxide), may be added to the mixture over a time period in a range offrom about 1 min to about 10 h; alternatively, from about 5 min to about6 h; or alternatively, from about 10 min to about 2 h. The mixture maythen be agitated for a time period in a range of from 10 min to about 24h; alternatively, from about 30 min to about 12 h; alternatively, fromabout 1 h to about 4 h; or alternatively, from about 2 h to about 3 h.The mixture may be sparged with the inert gas (e.g., nitrogen), for atime period in a range of from 5 min to about 24 h; alternatively, fromabout 10 min to about 12 h; alternatively, from about 30 min to about 4h; or alternatively, from about 1 h to about 4 h.

In a particular aspect, the process of producing a C₂₀₊ polysulfidescrude product comprises collecting a C₂₀₊ polysulfides crude product.The C₂₀₊ polysulfides crude product may be collected by any suitableliquid/solid separation technique known to the ordinary skilled artisan.Non-limiting examples of techniques for collecting the C₂₀₊ polysulfidescrude product include filtration (e.g., gravity, in-line, membrane,pressure, vacuum), centrifugation, gravimetric settling, hydrocyclonemethods, sedimentation, or combinations thereof. In an aspect,subsequent to sparging the mixture with the inert gas, the mixture maybe cooled to a temperature in a range of from about 15° C. to about 50°C., or alternatively, from about 20° C. to about 35° C. to form a cooledmixture. In a further aspect, the cooled mixture may be filtered tocollect the C₂₀₊ polysulfides crude product. Alternatively, prior tocollecting the C₂₀₊ polysulfides crude product, activated carbon of thetype disclosed herein is added to the cooled mixture and the temperatureof the cooled mixture is raised to a temperature in a range of fromabout 40° C. to about 80° C.; or alternatively, from about 50° C. toabout 70° C. The mixture is then agitated for a time period in a rangeof from 10 min to about 12 h; alternatively, from about 1 h to about 4h; or alternatively, from about 2 h to about 3 h. The process furthercomprises cooling the mixture to a temperature in a range of from about15° C. to about 50° C., or alternatively, from about 20° C. to about 35°C. and collecting (e.g., filtering), the C₂₀₊ polysulfides crudeproduct.

In an aspect, a feedstock comprising branched C₁₀₊ mercaptans (e.g., afirst C₁₀ to C₃₀ mercaptans feedstock or a second C₁₀ to C₃₀ mercaptansfeedstock) and a sulfur-containing material can be reacted to produce aC₂₀₊ crude product wherein a mercaptan conversion is achieved. In anaspect, the mercaptan conversion achieved is equal to or greater thanabout 70%, alternatively equal to or greater than about 75%,alternatively equal to or greater than about 80%, alternatively equal toor greater than about 85%, or alternatively equal to or greater thanabout 90%. For purposes of the disclosure herein, a mercaptan conversionrefers to the mol % of mercaptans that have reacted during the reactionbetween the sulfur-containing material (e.g., elemental sulfur) and thefeedstock in a reactor, with respect to the amount of mercaptansintroduced into the reactor during the same time period.

As noted previously, any suitable feedstock comprising branched C₁₀₊mercaptans as described herein (e.g., a first C₁₀ to C₃₀ mercaptansfeedstock or a second C₁₀ to C₃₀ mercaptans feedstock) can be reactedwith a sulfur-containing material in the presence of a catalyst toproduce a branched C₂₀₊ polysulfides crude product. The branched C₂₀₊polysulfides crude product can be further refined (e.g., distilled orotherwise separated into one or more fractions such as lights,intermediate, and heavies) to yield various compositions describedherein. As described in more detail herein, the type and/or amounts ofthe constituent components that form the branched C₂₀₊ polysulfidescrude product can vary depending upon the feedstock (e.g., the amountand types of mercaptans therein), the reaction conditions, the catalystsemployed, etc., and the ordinary skilled artisan can tailor the postreactor processing of the branched C₂₀₊ polysulfides crude product toaccount for the specific compounds present in a given branched C₂₀₊polysulfides crude product to yield various desired products andcompositions of the types described herein.

Upon completion of the reaction of a feedstock comprising branched C₁₀₊mercaptans with a sulfur-containing material, a reactor effluent may becollected (e.g., filtered) to yield a branched C₂₀₊ polysulfides crudeproduct, as previously described herein. The term “branched C₂₀₊polysulfides crude product” or “branched C₂₀₊ polysulfides crudeproduct” refers to an unrefined effluent stream collected from thereaction process (e.g., filtered), and in particular to an effluentstream that has not undergone any additional post-reactor processingsuch as flashing, distillation, or other separation techniques orprocesses to remove any components from the effluent stream other thanthe initial removal of by-products and/or solid reaction components(e.g., via filtering).

The branched C₂₀₊ polysulfides crude product comprises branched C₂₀ toC₆₀ polysulfides and branched C₂₀ to C₆₀ monosulfides formed by thereaction of one or more branched C₁₀ to C₃₀ mercaptans and the asulfur-containing material and the structures of these branched C₂₀ toC₆₀ polysulfides and branched C₂₀ to C₆₀ monosulfides are described inmore detail herein. In addition to branched C₂₀ to C₆₀ polysulfides andbranched C₂₀ to C₆₀ monosulfides, the branched C₂₀₊ polysulfides crudecomposition can comprise a number of other compounds such as unreactedmercaptans (e.g., unreacted branched C₁₀ to C₃₀ mercaptans, unreactedC₈₊ mercaptans), non-branched C₂₀ to C₆₀ polysulfides, non-branched C₂₀to C₆₀ monosulfides, non-C₂₀ to C₆₀ polysulfides, non-C₂₀ to C₆₀monosulfides, and other impurities (e.g., inert compounds). Theconstituent components contained within the branched C₂₀₊ polysulfidescrude product can vary depending upon the composition of the feedstock(e.g., an unpurified first C₁₀ to C₃₀ mercaptans feedstock as comparedto a purified second C₁₀ to C₃₀ mercaptans feedstock as describedherein) as well as reaction conditions, catalyst, etc. In variousaspects, a branched C₂₀₊ polysulfides crude product can comprise light,intermediate, and heavy fractions as described herein.

In an aspect, the branched C₂₀₊ polysulfides crude product can contain avariety of non-C₂₀ to C₆₀ polysulfides and non-C₂₀ to C₆₀ monosulfidescomponents (e.g., impurities) such as C₁₄ to C₁₉ polysulfidesrepresented by the general formula R¹⁹S—[S]_(n)—SR²⁰, wherein n is aninteger from 1 to 10, wherein R¹⁹ and R²⁰ are each independently afunctional group derived from a C₇₊ mercaptan, and wherein R¹⁹ and R²⁰are not both derived from a branched C₁₀₊ mercaptan; C₆₁ to C₇₈polysulfides represented by the general formula R¹⁹S—[S]_(n)—SR²⁰,wherein n is an integer from 1 to 10, wherein R¹⁹ and R²⁰ are eachindependently a functional group derived from a C₃₁ to C₃₈ mercaptan,and wherein R¹⁹ and R²⁰ are not both derived from a branched C₁₀₊mercaptan; C₁₄ to C₁₉ monosulfides represented by the general formulaR²¹—S—R²², wherein R²¹ and R²² are each independently a functional groupderived from a C₇₊ mercaptan, and wherein R²¹ and R²² are not bothderived from a branched C₁₀₊ mercaptan; or C₆₁ to C₇₈ monosulfidesrepresented by the general formula R²¹—S—R²², wherein R²¹ and R²² areeach independently a functional group derived from a C₃₁ to C₃₈mercaptan, and wherein R²¹ and R²² are not both derived from a branchedC₁₀₊ mercaptan.

In an aspect, the branched C₂₀₊ polysulfides crude product can contain avariety of non-branched C₂₀ to C₆₀ polysulfides and non-branched C₂₀ toC₆₀ monosulfides, such as C₂₀ to C₆₀ polysulfides represented by thegeneral formula R¹⁹S—[S]_(n)—SR²⁰ wherein n is an integer from 1 to 10,and wherein R¹⁹ and R²⁰ are each independently a non-branched C₁₀ to C₃₀alkyl group; and C₂₀ to C₆₀ monosulfides represented by the generalformula R²¹—S—R²² wherein R²¹ and R²² are each independently anon-branched C₁₀ to C₃₀ alkyl group. In a further aspect, thenon-branched C₂₀ to C₆₀ polysulfides can comprise C₂₀ to C₆₀polysulfides represented by the general formula R¹⁹S—[S]_(n)—SR²⁰wherein n is an integer from 1 to 10, wherein SR¹⁹ and SR²⁰ are eachindependently a functional group derived from a linear C₁₀ to C₃₀mercaptan represented by Structure M-1, Structure N-1, Structure O-1, orStructure P-1, as previously disclosed herein, and wherein R⁹ is a C₁ toC₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group, alternatively aC₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkyl group,alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ to C₁₇alkyl group, as previously disclosed herein; and the non-branched C₂₀ toC₆₀ monosulfides can comprise C₂₀ to C₆₀ monosulfides represented by thegeneral formula R²¹—S—R²² wherein R²¹ and R²² are each independently afunctional group derived from a linear C₁₀ to C₃₀ olefin represented byStructure Q-1, Structure R-1, or Structure S-1, as previously disclosedherein, wherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁alkyl group, alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅to C₂₁ alkyl group, alternatively a C₇ to C₁₉ alkyl group, oralternatively a C₉ to C₁₇ alkyl group.

In a further aspect, the branched C₂₀₊ polysulfides crude product cancontain a variety of non-mercaptan impurities selected from the groupconsisting of C₈ to C₇₈ olefins, C₈ to C₁₄ alkanes, cyclohexane,methylcyclopentane, methylcyclohexane, benzene, toluene, ethylbenzene,xylene, mesitylene, hexamethylbenzene, C₄ to C₁₂ alcohols,2-ethyl-1-hexanol, and 2-ethylhexyl-2-ethylhexanoate, and combinationsthereof.

In an aspect, a process of reacting a feedstock comprising branched C₁₀₊mercaptans and a sulfur-containing material to produce a C₂₀₊ crudeproduct can further comprise recovering a process product from thebranched C₂₀₊ polysulfides crude product, wherein the process productcan comprise branched C₂₀₊ polysulfides and/or branched C₂₀₊monosulfides, wherein the branched C₂₀₊ polysulfides comprise branchedC₂₀ to C₆₀ polysulfides represented by the general formulaR¹⁵S¹—[S]_(n)—S²R¹⁶ wherein n is an integer from 1 to 10, wherein thebranched C₂₀₊ monosulfides comprise branched C₂₀ to C₆₀, monosulfidesrepresented by the general formula R¹⁷—S—R¹⁸, wherein R¹⁵, R¹⁶, R¹⁷, andR¹⁸ are each independently an alkyl group, and wherein the alkyl groupcomprises a branched C₁₀ to C₃₀ alkyl group as disclosed herein.

In an aspect, the process product can comprise a branched C₂₀₊polysulfides composition (heavy fraction; primary reaction product), abranched C₂₀₊ monosulfides composition (intermediate fraction; sidereaction product), a branched C₂₀₊ polysulfides/branched C₂₀₊monosulfides composition (intermediate and heavy fractions; primary andside reaction products), or combinations thereof.

In an aspect, a branched C₂₀₊ polysulfides crude product comprisingbranched C₂₀₊ polysulfides and branched C₂₀₊ monosulfides as disclosedherein can be separated into two or more fractions (e.g., lightfraction, intermediate fraction, heavy fraction, etc.) by any process orunit operation known in the art. For example, a branched C₂₀₊polysulfides crude product can be processed (e.g., distilled) to removea fraction of light compounds. Alternatively, a branched C₂₀₊polysulfides crude product can be processed to recover both a lightfraction and an intermediate fraction (e.g., a rough cut), followed byfurther processing to obtain one or more fine cuts. Alternatively, abranched C₂₀₊ polysulfides crude product can be processed to recover aheavy fraction (e.g., a C₂₀₊ polysulfides fraction). Alternatively, abranched C₂₀₊ polysulfides crude product can be processed to separateout any combination of a light fraction, an intermediate fraction (e.g.,comprising C₂₀₊ monosulfides, including branched C₂₀₊ monosulfides), anda heavy fraction (e.g., comprising C₂₀₊ polysulfides, including branchedC₂₀₊ polysulfides). Furthermore, a light, intermediate or heavy fraction(e.g., a rough cut) can be further processed or parsed to obtain one ormore desired fine cuts (e.g., a C₂₀ to C₆₀ polysulfides fraction).Alternatively, a branched C₂₀₊ polysulfides crude product can beseparated to produce a high-purity C₂₀₊ polysulfides stream and/or ahigh-purity C₂₀₊ monosulfides (e.g., to obtain a desired fine cut orfraction such as a C₂₀ to C₆₀ polysulfides fraction). Further, theseseparated streams can be blended in any combination of ratios to producea mixture with specific concentrations of one of more components (e.g.,desired blend ratios of branched C₂₀₊ polysulfides and/or branched C₂₀₊monosulfides, for example to aid in a particular end use). The unitoperations/processes used for these separations are known to one ofskill and the art and include, but are not limited to, distillation,fractionation, flashing, stripping, and absorption, and others. The unitoperation conditions, such as for example, temperature, pressure, flowrates, and others at which these unit operations produce one or more ofthe desired fractions can be determined by one of ordinary skill in theart.

In an aspect, a light fraction is removed from the C₂₀₊ polysulfidesmercaptans crude composition, for example by flashing, distillation,fractionation, stripping, absorption, etc.

In an aspect, the light fraction removed from the branched C₂₀₊polysulfides crude product can comprise at least about 90 wt. %,alternatively at least about 92 wt. %, alternatively at least about 95wt. %, alternatively at least about 96 wt. %, alternatively at leastabout 97 wt. %, alternatively at least about 98 wt. %, or alternativelyat least about 99 wt. % C¹⁹⁻ metasulfides based on the total weight ofthe light fraction, wherein the C¹⁹⁻ metasulfides comprise C¹⁹⁻polysulfides, C¹⁹⁻ monosulfides, or a combination thereof. In a furtheraspect, the light fraction removed from the branched C₂₀₊ polysulfidescrude product can comprise at least about 90 wt. %, alternatively atleast about 92 wt. %, alternatively at least about 95 wt. %,alternatively at least about 96 wt. %, alternatively at least about 97wt. %, alternatively at least about 98 wt. %, or alternatively at leastabout 99 wt. % unreacted mercaptans based on the total weight of thelight fraction, wherein the unreacted mercaptans comprise unreacted C₁₀₊mercaptans, unreacted C⁹⁻ mercaptans, or a combination thereof. In afurther aspect, the light fraction removed from the branched C₂₀₊polysulfides crude product can comprise at least about 90 wt. %,alternatively at least about 92 wt. %, alternatively at least about 95wt. %, alternatively at least about 96 wt. %, alternatively at leastabout 97 wt. %, alternatively at least about 98 wt. %, or alternativelyat least about 99 wt. % C⁹⁻ compounds, based on the total weight of thelight fraction. Non-limiting examples of C⁹⁻ compounds include C⁹⁻monoolefins, C⁹⁻ alkanes, cyclohexane, methylcyclopentane,methylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene,C⁹⁻ alcohols, 2-ethyl-1-hexanol, and the like, or combinations thereof.In an aspect, the light fraction removed from the branched C₂₀₊polysulfides crude product can comprise less than about 10 wt. %,alternatively less than about 5 wt. %, alternatively less than about 4wt. %, alternatively at less than about 3 wt. %, alternatively less thanabout 2 wt. %, or alternatively less than about 1 wt. % C₂₀₊ compounds,based on the total weight of the light fraction. Non-limiting examplesof C₂₀₊ compounds include C₂₀₊ polysulfides, C₂₀₊ monosulfides, C₂₀₊monoolefins and C₂₀₊ alkanes.

Following removal of the lights (for example, via flashing) from thebranched C₂₀₊ polysulfides crude product, a combined intermediate andheavy fraction (i.e., C₂₀₊ polysulfides and C₂₀₊ monosulfides), canremain, and the combined intermediate and heavy fraction can be used “asis” or can be further processed, for example separated or split intoseparate intermediate and heavy fractions (and said separateintermediate and heavy fractions can be subsequently recombined invarious blends and associated blend ratios), as described in more detailherein. In an aspect, the combined intermediate and heavy fractionformed by removal of the light fraction from the branched C₂₀₊polysulfides crude product can comprise less than about 15 wt. %,alternatively less than about 10 wt. %, alternatively less than about 9wt. %, alternatively less than about 8 wt. %, alternatively less thanabout 7 wt. %, alternatively less than about 6 wt. %, alternatively lessthan about 5 wt. %, alternatively less than about 4 wt. %, alternativelyless than about 3 wt. %, alternatively less than about 2 wt. %, oralternatively less than about 1 wt. % C⁹⁻ products, based on the totalweight of the combined intermediate and heavy fraction.

In an aspect, a combined intermediate and heavy fraction (i.e., C₂₀₊polysulfides and C₂₀₊ monosulfides) recovered from the branched C₂₀₊polysulfides crude product can comprise (A) at least about 50 wt. %,alternatively at least about 60 wt. %, alternatively at least about 70wt. %, alternatively at least about 80 wt. %, alternatively at leastabout 90 wt. %, alternatively at least about 95 wt. %, or alternativelyat least about 99 wt. % polysulfides, based on the total weight of thecombined intermediate and heavy fraction; wherein at least about 50 wt.%, alternatively at least about 60 wt. %, alternatively at least about70 wt. %, alternatively at least about 75 wt. %, alternatively at leastabout 80 wt. %, or alternatively at least about 85 wt. % of thepolysulfides can be branched C₂₀ to C₆₀ polysulfides selected from thegroup consisting of a branched C₂₀ to C₆₀ polysulfide represented bygeneral formula R¹⁵S¹—[S]_(n)S²R¹⁶, wherein n is an integer from 1 to10, wherein R¹⁵ and R¹⁶ can each independently be a branched C₁₀ to C₃₀alkyl group represented by Structure K30-A, Structure K30-B, StructureK30-C, Structure K30-D, Structure K30-E, Structure K30-F, StructureK30-G, or Structure K30-H, wherein * designates an S¹ atom of an R¹⁵S¹group or an S² atom of an R¹⁶S² group, and wherein R⁹ is a C₁ to C₂₁alkyl group, alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkyl group, alternativelya C₇ to C₁₉ alkyl group, or alternatively a C₉ to C₁₇ alkyl group; and(B) at least about 10 wt. %, alternatively at least about 15 wt. %,alternatively at least about 20 wt. %, alternatively at least about 25wt. %, or alternatively at least about 30 wt. % monosulfides based onthe total weight of the combined intermediate and heavy fraction;wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at leastabout 85 wt. % of the monosulfides can be a branched C₂₀ to C₆₀monosulfide represented by general formula R¹⁷—S—R¹⁸, wherein R¹⁷ andR¹⁸ can each independently be a branched C₁₀ to C₃₀ alkyl grouprepresented by Structure K30-A, Structure K30-B, Structure K30-C,Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, orStructure K30-H, wherein * designates an attachment point with a sulfuratom of the branched C₂₀ to C₆₀ monosulfide, and wherein R⁹ is a C₁ toC₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group, alternatively aC₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkyl group,alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ to C₁₇alkyl group.

In an aspect, the branched C₂₀₊ polysulfides crude product can beflashed to remove a light fraction as described herein to produce acombined intermediate and heavy fraction (i.e., C₂₀₊ polysulfides andC₂₀₊ monosulfides), comprising: (A) at least about 25, 30, 35, 40, 45,50, 55, 60, 65, 70, 75, 80, or 85 wt. % branched C₂₀₊ polysulfidesselected from the group consisting of a branched C₂₀ to C₆₀ polysulfiderepresented by structure R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integerfrom 1 to 10, wherein R¹⁵ and R¹⁶ can each independently be a branchedC₁₀ to C₃₀ alkyl group represented by Structure K30-A, Structure K30-B,Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F,Structure K30-G, or Structure K30-H, wherein * designates an S¹ atom ofan R¹⁵S¹ group or an S² atom of an R¹⁶S² group, and wherein R⁹ is a C₁to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group, alternativelya C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkyl group,alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ to C₁₇alkyl group; and (B) at least about 5, 10, 15, 20, 25, or 30 wt. %branched C₂₀₊ monosulfides represented by general formula R¹⁷—S—R¹⁸,wherein R¹⁷ and R¹⁸ can each independently be a branched C₁₀ to C₃₀alkyl group represented by Structure K30-A, Structure K30-B, StructureK30-C, Structure K30-D, Structure K30-E, Structure K30-F, StructureK30-G, or Structure K30-H, wherein * designates an attachment point witha sulfur atom of the branched C₂₀₊ monosulfide, and wherein R⁹ is a C₁to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group, alternativelya C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkyl group,alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ to C₁₇alkyl group.

In an aspect, the branched C₂₀₊ polysulfides crude product can beflashed to remove a lights fraction as described herein to produce acombined intermediate and heavy fraction (i.e., C₂₀₊ polysulfides andC₂₀₊ monosulfides), comprising: (A) from at least about 50 wt. % to atleast about 90 wt. %, alternatively from at least about 55 wt. % to atleast about 85 wt. %, or alternatively from at least about 60 wt. % toat least about 80 wt. % polysulfides, wherein at least about 50 wt. %,alternatively at least about 60 wt. %, alternatively at least about 70wt. %, alternatively at least about 75 wt. %, alternatively at leastabout 80 wt. %, or alternatively at least about 85 wt. % of thepolysulfides can be branched C₂₀ to C₆₀ polysulfides selected from thegroup consisting of a branched C₂₀ to C₆₀ polysulfide represented bygeneral formula R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integer from 1 to10, wherein R¹⁵ and R¹⁶ can each independently be a branched C₁₀ to C₃₀alkyl group represented by Structure K30-A, Structure K30-B, StructureK30-C, Structure K30-D, Structure K30-E, Structure K30-F, StructureK30-G, or Structure K30-H, wherein * designates an S¹ atom of an R¹⁵S¹group or an S² atom of an R¹⁶S² group, and wherein R⁹ is a C₁ to C₂₁alkyl group, alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkyl group, alternativelya C₇ to C₁₉ alkyl group, or alternatively a C₉ to C₁₇ alkyl group; and(B) from at least about 10 wt. % to at least about 30 wt. %,alternatively from at least about 10 wt. % to at least about 25 wt. %,alternatively from at least about 12.5 wt. % to at least about 22.5 wt.%, or alternatively from at least about 15 wt. % to at least about 20wt. % monosulfides, wherein at least about 50 wt. %, alternatively atleast about 60 wt. %, alternatively at least about 70 wt. %,alternatively at least about 75 wt. %, alternatively at least about 80wt. %, or alternatively at least about 85 wt. % of the monosulfides canbe a branched C₂₀ to C₆₀ monosulfide represented by general formulaR¹⁷—S—R¹⁸, wherein R¹⁷ and R¹⁸ can each independently be a branched C₁₀to C₃₀ alkyl group represented by Structure K30-A, Structure K30-B,Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F,Structure K30-G, or Structure K30-H, wherein * designates an attachmentpoint with a sulfur atom of the branched C₂₀ to C₆₀ monosulfide, andwherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkylgroup, alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁alkyl group, alternatively a C₇ to C₁₉ alkyl group, or alternatively aC₉ to C₁₇ alkyl group.

In an aspect, the branched C₂₀₊ polysulfides crude product can beflashed to remove a light fraction and subsequently further separated toproduce an intermediate fraction and a heavy fraction. Each of theintermediate fraction and the heavy fraction recovered from the branchedC₂₀₊ polysulfides crude product can then be optionally further processed(e.g., polished) and mixed in any appropriate ratio to produce blendedcompositions, as previously described herein for crude compositionsderived from branched C₁₀₊ monoolefins.

In an aspect, the heavy fraction recovered from the branched C₂₀₊polysulfides crude product can comprise at least about 25 wt. %,alternatively at least about 30 wt. %, alternatively at least about 40wt. %, alternatively at least about 50 wt. %, alternatively at leastabout 75 wt. %, or alternatively at least about 85 wt. % C₂₀₊polysulfides, based on the total weight of the heavy fraction, whereinthe C₂₀₊ polysulfides are branched C₂₀ to C₆₀ polysulfides as disclosedherein.

In an aspect, an intermediate fraction recovered from the branched C₂₀₊polysulfides crude product can comprise at least about 5, 10, 15, 20,25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt. %, C₂₀₊monosulfides, based on the total weight of the intermediate fraction,wherein the C₂₀₊ monosulfides are branched C₂₀ to C₆₀ monosulfides asdisclosed herein.

In an aspect, the branched C₂₀₊ polysulfides crude product can beseparated into light, intermediate, and heavy fractions by distillation,for example in a single distillation column having a light fractionrecovered as an overhead stream, an intermediate fraction (e.g.,comprising C₂₀₊ monosulfides) recovered as a side stream, and a heavyfraction (e.g., comprising C₂₀₊ polysulfides) recovered as a bottomstream. In alternative aspects, the separation can be in sequentialsteps such as removal of the lights fraction in a first distillationcolumn, followed by separation of the intermediate fraction (e.g.,comprising C₂₀₊ monosulfides) as an overhead stream in a seconddistillation column and the heavy fraction (e.g., comprising C₂₀₊polysulfides) as a bottom stream of the second distillation column.These “rough-cut” light, intermediate, and heavy streams can be used “asis” or they can be further processed (e.g., further refined or polished,for example by additional distillation or other separation techniques toproduce “fine-cuts”) and/or blended to obtain a variety of products thatare salable or otherwise available for a variety of end uses such asmining ore collector compositions or chain transfer agents. For example,a variety of C₂₀₊ polysulfides compositions, C₂₀₊ monosulfidescompositions, and C₂₀₊ metasulfides compositions (i.e., mixed C₂₀₊polysulfides/C₂₀₊ monosulfides compositions) of the type disclosedherein can be produced as disclosed herein.

In aspects where the mercaptan feedstock (e.g., mercaptan feedstockreacted with a sulfur-containing material to produce the branched C₂₀₊polysulfides crude product) comprises C₁₀ to C₁₉ mercaptans, theintermediate fraction comprises C₂₀ to C₃₈ monosulfides, and the heavyfraction comprises C₂₀ to C₃₈ polysulfides.

In aspects where the mercaptan feedstock (e.g., mercaptan feedstockreacted with a sulfur-containing to produce the branched C₂₀₊polysulfides crude product) comprises C₂₀ to C₃₀ mercaptans, theintermediate fraction comprises C₄₀ to C₆₀ monosulfides, and the heavyfraction comprises C₄₀ to C₆₀ polysulfides.

In aspects where the mercaptan feedstock (e.g., mercaptan feedstockreacted with a sulfur-containing material to produce the branched C₂₀₊polysulfides crude product) comprises C₁₀ to C₃₀ mercaptans, theintermediate and heavy fractions recovered by distillation can comprisemercaptans and sulfides as follows. In some aspects, the intermediatefraction can comprise C₁₀ to C₁₉ monosulfides, and the heavy fractioncan comprise C₂₀ to C₃₀ monosulfides and C₂₀ to C₆₀ polysulfides. Inother aspects, intermediate fraction can comprise C₁₀ to C₃₀monosulfides and C₂₀ to C₃₀ polysulfides, and the heavy fraction cancomprise C₃₁ to C₆₀ polysulfides. In yet other aspects, a firstintermediate fraction can comprise C₁₀ to C₁₉ monosulfides, a secondintermediate fraction can comprise C₂₀ to C₃₀ monosulfides and C₂₀ toC₃₀ polysulfides, and the heavy fraction can comprise C₃₁ to C₆₀polysulfides. Intermediate and heavy fractions comprising bothmonosulfides and polysulfides could be used as recovered (e.g., mixedmonosulfides/polysulfides compositions) or can be further processed toseparate and recover further monosulfides compositions and polysulfidescompositions.

In an aspect, an intermediate fraction can comprise at least about 25,30, 40, 50, 75, or 85 wt. % branched C₂₀₊ monosulfides. In such aspect,the branched C₂₀₊ monosulfides can be selected from the group consistingof a branched C₂₀ to C₆₀ monosulfide represented by general formulaR¹⁷—S—R¹⁸, wherein R¹⁷ and R¹⁸ can each independently be a branched C₁₀to C₃₀ alkyl group represented by Structure K30-A, Structure K30-B,Structure K30-C, Structure K30-D, Structure K30-E, Structure K30-F,Structure K30-G, or Structure K30-H, wherein * designates an attachmentpoint with a sulfur atom of the branched C₂₀ to C₆₀ monosulfide, andwherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁ alkylgroup, alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁alkyl group, alternatively a C₇ to C₁₉ alkyl group, or alternatively aC₉ to C₁₇ alkyl group.

In an aspect, the heavy fraction can comprise at least about 5, 10, 15,20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt. % branchedC₂₀₊ polysulfides. In such aspect, the branched C₂₀₊ polysulfides can beselected from the group consisting of a branched C₂₀ to C₆₀ polysulfiderepresented by general formula R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is aninteger from 1 to 10, wherein R¹⁵ and R¹⁶ can each independently be abranched C₁₀ to C₃₀ alkyl group represented by Structure K30-A,Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E,Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an S¹ atom of an R¹⁵S¹ group or an S² atom of an R¹⁶S² group,and wherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁alkyl group, alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅to C₂₁ alkyl group, alternatively a C₇ to C₁₉ alkyl group, oralternatively a C₉ to C₁₇ alkyl group.

In an aspect, a C₂₀₊ polysulfides composition can comprise C₂₀₊polysulfides, wherein at least a portion of the C₂₀₊ polysulfidescomprise branched C₂₀₊ polysulfides. Further for purposes of thedisclosure herein, branched C₂₀₊ polysulfides refer to polysulfides thatare represented by the general formula R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n isan integer from 1 to 10, wherein R¹⁵ and R¹⁶ are each a branched alkylgroup (i.e., a non-linear alkyl group, or in other words an alkyl groupsubstituted with alkyl substituents), and wherein R¹⁵ and R¹⁶ can eachindependently have from 10 to 30 carbon atoms, alternatively from 11 to30 carbon atoms, alternatively from 12 to 30 carbon atoms, alternativelyfrom 14 to 30 carbon atoms, alternatively from 16 to 28 carbon atoms, oralternatively from 18 to 26 carbon atoms. In an aspect, the branchedC₂₀₊ polysulfides of the present disclosure comprise branched C₂₀ to C₆₀polysulfides wherein the branched C₂₀ to C₆₀ polysulfides can comprise abranched C₂₀ to C₆₀ polysulfide represented by general formulaR¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integer from 1 to 10, wherein R¹⁵and R¹⁶ can each independently be a branched C₁₀ to C₃₀ alkyl grouprepresented by Structure K30-A, Structure K30-B, Structure K30-C,Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, orStructure K30-H, wherein * designates an S¹ atom of an R¹⁵S¹ group or anS² atom of an R¹⁶S² group, and wherein R⁹ is a C₁ to C₂₁ alkyl group,alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁ alkylgroup, alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉alkyl group, or alternatively a C₉ to C₁₇ alkyl group. For purposes ofthe disclosure herein a polysulfide (e.g., a branched C₂₀ to C₆₀polysulfide) will be referred to by the total number of carbon atoms, asopposed to the number of carbons of only one of the alkyl groups presentin the polysulfide. For example, wherein x is an integer from 3 to 12, aH₂₁C₁₀—S_(x)—C₁₀H₂₁ polysulfide will be referred to as a C₂₀ polysulfide(rather than a C₁₀ polysulfide); a H₂₅C₁₂—S_(x)—C₁₄H₂₉ polysulfide willbe referred to as a C₂₆ polysulfide (rather than a C₁₂ polysulfide or aC₁₄ polysulfide); a H₄₅C₂₂—S_(x)C₂₂H₄₅ polysulfide will be referred toas a C₄₄ polysulfide (rather than a C₂₂ polysulfide); etc. Thepolysulfides of the present disclosure comprise two alkyl groups linkedby a group of sulfur atoms comprising from two to twelve, oralternatively three to six sulfur atoms. Further, for purposes of thedisclosure herein, the specific number of sulfur atoms comprising thepolysulfide is not distinguished. For example, in regard to C₂₀polysulfides represented by the general formula H₂₁C₁₀S—[S]_(n)—SC₁₀H₂₁when n is 1, the corresponding C₂₀ trisulfide has formulaH₂₁C₁₀—SSS—C₁₀H₂₁; alternatively, when n is 2, the corresponding C₂₀tetrasulfide has formula H₂₁C₁₀—SSSS—C₁₀H₂₁; alternatively, when n is 3,the corresponding C₂₀ pentasulfide has formula H₂₁C₁₀—SSSSS—C₁₀H₂₁; etc.In such aspects, the C₂₀ trisulfide, the C₂₀ tetrasulfide, and the C₂₀pentasulfide are referred to as a C₂₀ polysulfide. In a further aspect,a polysulfide of the present disclosure may be termed a “MixedIntermediate Polysulfide” (MIPS) and described with an average number ofsulfur atoms within the polysulfide and a weight percentage of sulfurwithin the polysulfide. In a nonlimiting example, a C₂₀ polysulfidehaving an average molecular formula H₂₁C₁₀—{SSS}—C₁₀H₂₁ represents apolysulfide comprising an average of three sulfur atoms (i.e., “{ }”brackets indicate an average number of sulfur atoms) and furthercomprising 25 wt. % sulfur based on the formula weight of the averagemolecular formula and may be termed a MIPS 325. In a further nonlimitingexample, a C₂₀ polysulfide having an average molecular formulaH₂₁C₁₀—{SSSSS}—C₁₀H₂₁ represents a polysulfide comprising an average offive sulfur atoms and further comprising 37 wt. % sulfur based on theformula weight of the average molecular formula and may be termed a MIPS537. Further for purposes of the disclosure herein a compositioncomprising polysulfides, wherein at least a portion of the polysulfidesare branched C₂₀₊ polysulfides (e.g., branched C₂₀ to C₆₀ polysulfidesas disclosed herein) can also be referred to as a “branched C₂₀₊polysulfides composition.” In an aspect, the branched C₂₀₊ polysulfidescomposition can comprise any suitable amount of branched C₂₀ to C₆₀polysulfides.

In an aspect, the C₂₀₊ polysulfides can further comprise non-branchedC₂₀₊ polysulfides, such as linear C₂₀ to C₆₀ polysulfides represented bygeneral formula R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integer from 1 to10, wherein R¹⁵S¹ and R¹⁶S² can each independently be a functional groupderived from a mercaptan, wherein the mercaptan may be a C₁₀ to C₃₀mercaptan represented by Structure M-1, Structure N-1, Structure O-1, orStructure P-1, as previously disclosed herein, and wherein R⁹ is a C₁ toC₂₁ alkyl group, alternatively a C₂ to C₂₁ alkyl group, alternatively aC₃ to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkyl group,alternatively a C₇ to C₁₉ alkyl group, or alternatively a C₉ to C₁₇alkyl group.

In aspects where R⁹ is a methyl group, the C₂₀₊ polysulfides can furthercomprise non-branched C₁₀ polysulfides. The non-branched C₁₀polysulfides can be represented by general formula R¹⁵S¹—[S]_(n)—S²R¹⁶,wherein n is an integer from 1 to 10, wherein R¹⁵S¹ and R¹⁶S² can eachindependently be a functional group derived from a mercaptan, whereinthe mercaptan may be a C₁₀ mercaptan represented by Structure M,Structure N, Structure 0, or Structure P, as previously disclosedherein.

In some aspects, a C₂₀₊ polysulfides composition can comprise at leastabout 50 wt. %, alternatively at least about 60 wt. %, alternatively atleast about 70 wt. %, alternatively at least about 80 wt. %,alternatively at least about 90 wt. %, alternatively at least about 95wt. %, or alternatively at least about 99 wt. % C₂₀₊ polysulfides, basedon the total weight of the C₂₀₊ polysulfides composition; wherein atleast about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at least85 wt. % of the C₂₀₊ polysulfides can be C₂₀ to C₆₀ polysulfidesrepresented by the general formula R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is aninteger from 1 to 10, wherein R¹⁵ and R¹⁶ are each a branched alkylgroup, and wherein R¹⁵ and R¹⁶ can each independently have from 10 to 30carbon atoms, alternatively from 11 to 30 carbon atoms, alternativelyfrom 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms,alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26carbon atoms. In such aspects, the branched C₂₀ to C₆₀ polysulfides canbe selected from the group consisting of a branched C₂₀ to C₆₀polysulfide represented by the general formula R¹⁵S¹—[S]_(n)—S²R¹⁶,wherein n is an integer from 1 to 10, wherein R¹⁵ and R¹⁶ can eachindependently be a branched C₁₀ to C₃₀ alkyl group represented byStructure K30-A, Structure K30-B, Structure K30-C, Structure K30-D,Structure K30-E, Structure K30-F, Structure K30-G, or Structure K30-H,wherein * designates an S¹ atom of an R¹⁵S¹ group or an S² atom of anR¹⁶S² group, and wherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively aC₂ to C₂₁ alkyl group, alternatively a C₃ to C₂₁ alkyl group,alternatively a C₅ to C₂₁ alkyl group, alternatively a C₇ to C₁₉ alkylgroup, or alternatively a C₉ to C₁₇ alkyl group.

In other aspects, a C₂₀₊ polysulfides composition can comprise at leastabout 1 wt. %, alternatively at least about 5 wt. %, alternatively atleast about 10 wt. %, alternatively at least about 20 wt. %,alternatively at least about 30 wt. %, alternatively at least about 40wt. %, alternatively at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 80 wt. %, alternatively at least about 90 wt. %,alternatively at least about 95 wt. %, or alternatively at least about99 wt. % polysulfides, wherein at least a portion of the polysulfidescan be branched C₂₀ to C₆₀ polysulfides represented by the generalR¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integer from 1 to 10, wherein R¹⁵and R¹⁶ are each a branched alkyl group, and wherein R¹⁵ and R¹⁶ caneach independently have from 10 to 30 carbon atoms, alternatively from11 to 30 carbon atoms, alternatively from 12 to 30 carbon atoms,alternatively from 14 to 30 carbon atoms, alternatively from 16 to 28carbon atoms, or alternatively from 18 to 26 carbon atoms. In suchaspects, the branched C₂₀ to C₆₀ polysulfides can be selected from thegroup consisting of a branched C₂₀ to C₆₀ polysulfide represented bygeneral formula R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integer from 1 to10, wherein R¹⁵ and R¹⁶ can each independently be a branched C₁₀ to C₃₀alkyl group represented by Structure K30-A, Structure K30-B, StructureK30-C, Structure K30-D, Structure K30-E, Structure K30-F, StructureK30-G, or Structure K30-H, wherein * designates an S¹ atom of an R¹⁵S¹group or an S² atom of an R¹⁶S² group, and wherein R⁹ is a C₁ to C₂₁alkyl group, alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkyl group, alternativelya C₇ to C₁₉ alkyl group, or alternatively a C₉ to C₁₇ alkyl group.

In yet other aspects, a C₂₀₊ polysulfides composition can comprise atleast about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 80wt. %, alternatively at least about 90 wt. %, alternatively at leastabout 95 wt. %, or alternatively at least about 99 wt. % polysulfides;wherein at least about 50 wt. %, alternatively at least about 60 wt. %,alternatively at least about 70 wt. %, alternatively at least about 75wt. %, alternatively at least about 80 wt. %, or alternatively at least85 wt. % of the polysulfides can be branched C₂₀ to C₆₀ polysulfidesrepresented by the general formula R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is aninteger from 1 to 10, wherein R¹⁵ and R¹⁶ are each a branched alkylgroup, and wherein R¹⁵ and R¹⁶ can each independently have from 10 to 30carbon atoms, alternatively from 11 to 30 carbon atoms, alternativelyfrom 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms,alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26carbon atoms. In such aspects, the branched C₂₀ to C₆₀ polysulfides canbe selected from the group consisting of a branched C₂₀ to C₆₀polysulfide represented by general formula R¹⁵S¹—[S]_(n)—S²R¹⁶, whereinn is an integer from 1 to 10, wherein R¹⁵ and R¹⁶ can each independentlybe a branched C₁₀ to C₃₀ alkyl group represented by Structure K30-A,Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E,Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an S¹ atom of an R¹⁵S¹ group or an S² atom of an R¹⁶S² group,and wherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁alkyl group, alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅to C₂₁ alkyl group, alternatively a C₇ to C₁₉ alkyl group, oralternatively a C₉ to C₁₇ alkyl group.

In still yet other aspects, a C₂₀₊ polysulfides composition can compriseat least about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt. %polysulfides; wherein at least about 25, 30, 35, 40, 45, 50, 55, 60, 65,70, 75, 80, 85, 90, 95, or 99 wt. % of the polysulfides can be branchedC₂₀ to C₆₀ polysulfides represented by the general formulaR¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integer from 1 to 10, wherein R¹⁵and R¹⁶ are each a branched alkyl group, and wherein R¹⁵ and R¹⁶ caneach independently have from 10 to 30 carbon atoms, alternatively from11 to 30 carbon atoms, alternatively from 12 to 30 carbon atoms,alternatively from 14 to 30 carbon atoms, alternatively from 16 to 28carbon atoms, or alternatively from 18 to 26 carbon atoms. In suchaspects, the branched C₂₀ to C₆₀ polysulfides can be selected from thegroup consisting of a branched C₂₀ to C₆₀ polysulfide represented bygeneral formula R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integer from 1 to10, wherein R¹⁵ and R¹⁶ can each independently be a branched C₁₀ to C₃₀alkyl group represented by Structure K30-A, Structure K30-B, StructureK30-C, Structure K30-D, Structure K30-E, Structure K30-F, StructureK30-G, or Structure K30-H, wherein * designates an S¹ atom of an R¹⁵S¹group or an S² atom of an R¹⁶S² group, and wherein R⁹ is a C₁ to C₂₁alkyl group, alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkyl group, alternativelya C₇ to C₁₉ alkyl group, or alternatively a C₉ to C₁₇ alkyl group.

In still yet other aspects, a C₂₀₊ polysulfides composition can comprisefrom at least about 50 wt. % to at least about 90 wt. %, alternativelyfrom at least about 55 wt. % to at least about 85 wt. %, oralternatively from at least about 60 wt. % to at least about 80 wt. %polysulfides, wherein at least about 50 wt. %, alternatively at leastabout 60 wt. %, alternatively at least about 70 wt. %, alternatively atleast about 75 wt. %, alternatively at least about 80 wt. %, oralternatively at least about 85 wt. % of the polysulfides can bebranched C₂₀ to C₆₀ polysulfides represented by the general formulaR¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integer from 1 to 10, wherein R¹⁵and R¹⁶ are each a branched alkyl group, and wherein R¹⁵ and R¹⁶ caneach independently have from 10 to 30 carbon atoms, alternatively from11 to 30 carbon atoms, alternatively from 12 to 30 carbon atoms,alternatively from 14 to 30 carbon atoms, alternatively from 16 to 28carbon atoms, or alternatively from 18 to 26 carbon atoms. In suchaspects, the branched C₂₀ to C₆₀ polysulfides can be selected from thegroup consisting of a branched C₂₀ to C₆₀ polysulfide represented bygeneral formula R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integer from 1 to10, wherein R¹⁵ and R¹⁶ can each independently be a branched C₁₀ to C₃₀alkyl group represented by Structure K30-A, Structure K30-B, StructureK30-C, Structure K30-D, Structure K30-E, Structure K30-F, StructureK30-G, or Structure K30-H, wherein * designates an S¹ atom of an R¹⁵S¹group or an S² atom of an R¹⁶S² group, and wherein R⁹ is a C₁ to C₂₁alkyl group, alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkyl group, alternativelya C₇ to C₁₉ alkyl group, or alternatively a C₉ to C₁₇ alkyl group.

In still yet other aspects, a C₂₀₊ polysulfides composition can consistof, or consist essentially of, branched C₂₀ to C₆₀ polysulfidesrepresented by the general formula R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is aninteger from 1 to 10, wherein R¹⁵ and R¹⁶ are each a branched alkylgroup, and wherein R¹⁵ and R¹⁶ can each independently have from 10 to 30carbon atoms, alternatively from 11 to 30 carbon atoms, alternativelyfrom 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms,alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26carbon atoms. In such aspects, the branched C₂₀ to C₆₀ polysulfides canbe selected from the group consisting of a branched C₂₀ to C₆₀polysulfide represented by general formula R¹⁵S¹—[S]_(n)—S²R¹⁶, whereinn is an integer from 1 to 10, wherein R¹⁵ and R¹⁶ can each independentlybe a branched C₁₀ to C₃₀ alkyl group represented by Structure K30-A,Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E,Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an S¹ atom of an R¹⁵S¹ group or an S² atom of an R¹⁶S² group,and wherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁alkyl group, alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅to C₂₁ alkyl group, alternatively a C₇ to C₁₉ alkyl group, oralternatively a C₉ to C₁₇ alkyl group.

In still yet other aspects, a C₂₀₊ polysulfides composition can compriseat least about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,75, 80, 85, 90, 95, or 99 wt. % branched C₂₀ to C₆₀ polysulfidesrepresented by the general formula R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is aninteger from 1 to 10, wherein R¹⁵ and R¹⁶ are each a branched alkylgroup, and wherein R¹⁵ and R¹⁶ can each independently have from 10 to 30carbon atoms, alternatively from 11 to 30 carbon atoms, alternativelyfrom 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms,alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26carbon atoms. In such aspects, the branched C₂₀ to C₆₀ polysulfides canbe selected from the group consisting of a branched C₂₀ to C₆₀polysulfide represented by general formula R¹⁵S¹—[S]_(n)—S²R¹⁶, whereinn is an integer from 1 to 10, wherein R¹⁵ and R¹⁶ can each independentlybe a branched C₁₀ to C₃₀ alkyl group represented by Structure K30-A,Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E,Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an S¹ atom of an R¹⁵S¹ group or an S² atom of an R¹⁶S² group,and wherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁alkyl group, alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅to C₂₁ alkyl group, alternatively a C₇ to C₁₉ alkyl group, oralternatively a C₉ to C₁₇ alkyl group.

In still yet other aspects, a C₂₀₊ polysulfides composition can comprisepolysulfides, wherein at least about 50, 55, 60, 65, 70, 75, 80, 85, 90,95, or 99 wt. % of the polysulfides are branched C₂₀ to C₆₀ polysulfidesrepresented by the general formula R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is aninteger from 1 to 10, wherein R¹⁵ and R¹⁶ are each a branched alkylgroup, and wherein R¹⁵ and R¹⁶ can each independently have from 10 to 30carbon atoms, alternatively from 11 to 30 carbon atoms, alternativelyfrom 12 to 30 carbon atoms, alternatively from 14 to 30 carbon atoms,alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26carbon atoms. In such aspects, the branched C₂₀ to C₆₀ polysulfides canbe selected from the group consisting of a branched C₂₀ to C₆₀polysulfide represented by general formula R¹⁵S¹—[S]_(n)—S²R¹⁶, whereinn is an integer from 1 to 10, wherein R¹⁵ and R¹⁶ can each independentlybe a branched C₁₀ to C₃₀ alkyl group represented by Structure K30-A,Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E,Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an S¹ atom of an R¹⁵S¹ group or an S² atom of an R¹⁶S² group,and wherein R⁹ is a C₁ to C₂₁ alkyl group, alternatively a C₂ to C₂₁alkyl group, alternatively a C₃ to C₂₁ alkyl group, alternatively a C₅to C₂₁ alkyl group, alternatively a C₇ to C₁₉ alkyl group, oralternatively a C₉ to C₁₇ alkyl group.

In an aspect, a C₂₀₊ monosulfides composition can comprise monosulfides,wherein at least a portion of the monosulfides comprise C₂₀₊monosulfides, and wherein at least a portion of the C₂₀₊ monosulfidescomprise branched C₂₀ to C₆₀ monosulfides. The term monosulfide as usedherein refers to a thioether that is characterized by the generalformula R¹⁷—S—R¹⁸, wherein R¹⁷ and R¹⁸ are alkyl groups. The termmonosulfide is used herein in place of the term sulfide, which is acommon name for a thioether, to distinguish a sulfide comprising asingle sulfur atom (i.e., monosulfide), from a sulfide comprising morethan one sulfur atom (i.e., polysulfide). In a further aspect, the C₂₀₊monosulfides composition of the present disclosure is comparable to aC₂₀₊ sulfides composition previously disclosed herein that is producedby reacting, in a reactor, a sulfur source (e.g., H₂S) and a feedstockcomprising one or more branched C₁₀₊ monoolefins in the presence of aninitiating agent. In a further aspect, the components of the C₂₀₊monosulfides composition of the present disclosure, (e.g., themonosulfides, the C₂₀₊ monosulfides and the branched C₂₀ to C₆₀monosulfides) are identical to the components of the C₂₀₊ sulfidescomposition previously disclosed herein, (e.g., the sulfides, the C₂₀₊sulfides and the branched C₂₀ to C₆₀ sulfides, respectively). It will beappreciated that the C₂₀₊ monosulfides composition is thoroughlydescribed as the C₂₀₊ sulfides composition that is produced by reacting,in a reactor, a sulfur source (e.g., H₂S) and a feedstock comprising oneor more branched C₁₀₊ monoolefins in the presence of an initiating agentas previously disclosed herein. For the sake of clarity and brevity nofurther description of the C₂₀₊ monosulfides composition is providedherein.

In an aspect, a C₂₀₊ polysulfides/C₂₀₊ monosulfide composition (i.e., aC₂₀₊ metasulfides composition) can comprise one or more polysulfides andone or more monosulfides of the type disclosed herein. For purposes ofthe disclosure herein, a composition comprising (i) polysulfides,wherein at least a portion of the polysulfides are branched C₂₀ to C₆₀polysulfides, and (ii) monosulfides, wherein at least a portion of themonosulfides are branched C₂₀ to C₆₀ monosulfides, can also be referredto as a “branched C₂₀₊ polysulfides/branched C₂₀₊ monosulfidescomposition.” In an aspect, the C₂₀₊ polysulfides/C₂₀₊ monosulfidescomposition can comprise any suitable amount of branched C₁₀ to C₃₀polysulfides and any suitable amount of branched C₂₀ to C₆₀monosulfides.

In an aspect, a C₂₀₊ polysulfides/C₂₀₊ monosulfides composition cancomprise (A) at least about 1 wt. %, alternatively at least about 5 wt.%, alternatively at least about 10 wt. %, alternatively at least about15 wt. %, alternatively at least about 20 wt. %, alternatively at leastabout 25 wt. %, alternatively at least about 30 wt. %, alternatively atleast about 40 wt. %, alternatively at least about 50 wt. %,alternatively at least about 60 wt. %, alternatively at least about 70wt. %, alternatively at least about 80 wt. %, alternatively at leastabout 90 wt. %, alternatively at least about 95 wt. %, or alternativelyat least about 99 wt. % polysulfides, wherein at least a portion of thepolysulfides can be branched C₂₀ to C₆₀ polysulfides represented by thegeneral formula R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integer from 1 to10; and (B) at least about 1 wt. %, alternatively at least about 5 wt.%, alternatively at least about 10 wt. %, alternatively at least about20 wt. %, alternatively at least about 30 wt. %, alternatively at leastabout 40 wt. %, alternatively at least about 50 wt. %, alternatively atleast about 60 wt. %, alternatively at least about 70 wt. %,alternatively at least about 80 wt. %, alternatively at least about 90wt. %, alternatively at least about 95 wt. %, or alternatively at leastabout 99 wt. % monosulfides, wherein at least a portion of themonosulfides can be branched C₂₀ to C₆₀ monosulfides represented bygeneral formula R¹⁷—S—R¹⁸; wherein R¹⁵, R¹⁶, R¹⁷, and R¹⁸ can eachindependently be a branched alkyl group comprising from 10 to 30 carbonatoms, alternatively from 11 to 30 carbon atoms, alternatively from 12to 30 carbon atoms, alternatively from 14 to 30 carbon atoms,alternatively from 16 to 28 carbon atoms, or alternatively from 18 to 26carbon atoms. In such aspect, R¹⁵ and R¹⁶ can each independently be abranched C₁₀ to C₃₀ alkyl group represented by Structure K30-A,Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E,Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an S¹ atom of an R¹⁵S¹ group or an S² atom of an R¹⁶S² group,and R¹⁷ and R¹⁸ can each independently be a branched C₁₀ to C₃₀ alkylgroup represented by Structure K30-A, Structure K30-B, Structure K30-C,Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, orStructure K30-H, wherein * designates an attachment point with a sulfuratom of the branched C₂₀ to C₆₀ monosulfide, wherein R⁹ is a C₁ to C₂₁alkyl group, alternatively a C₂ to C₂₁ alkyl group, alternatively a C₃to C₂₁ alkyl group, alternatively a C₅ to C₂₁ alkyl group, alternativelya C₇ to C₁₉ alkyl group, or alternatively a C₉ to C₁₇ alkyl group.

In an aspect, a C₂₀₊ polysulfides/C₂₀₊ monosulfides composition cancomprise C₂₀ to C₆₀ polysulfides represented by the general formulaR¹⁵S¹—[S]_(n)—S²R¹⁶, and/or C₂₀ to C₆₀ monosulfides represented by thegeneral formula R¹⁷—S—R¹⁸ that are formed by reacting a mercaptanfeedstock comprising mercaptans with a sulfur-containing material (e.g.,elemental sulfur), as described in more detail herein, wherein themercaptans present in the mercaptan feedstock provide the alkyl grouprepresented by R¹⁵, R¹⁶, R¹⁷, and R¹⁸. In such aspects, the R¹⁵ and R¹⁶groups of the C₂₀ to C₆₀ polysulfides and/or the R¹⁷ and R¹⁸ groups ofthe C₂₀ to C₆₀ monosulfides are provided by or derived from thecounterpart R¹⁵, R¹⁶, R¹⁷, and R¹⁸ groups present in the mercaptans inthe mercaptan feedstock. In an aspect, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ can eachindependently be an alkyl group, wherein at least a portion of the alkylgroups can comprise a functional group derived from a mercaptan, whereinthe mercaptan is present in a feedstock as disclosed herein (e.g., afirst C₁₀ to C₃₀ mercaptans feedstock; a second C₁₀ to C₃₀ mercaptansfeedstock).

In an aspect, a process of reacting branched mercaptans to producepolysulfides as disclosed herein can advantageously be more facile thanan otherwise similar process comprising tertiary mercaptans. Forexample, tert-butyl polysulfide and tert-dodecyl polysulfide areproduced from the tertiary mercaptans tert-butyl mercaptan andtert-dodecyl mercaptan, respectively, by a process similar to the onedisclosed herein. Steric bulk proximal to the sulfur atom of thetertiary mercaptans decreases the reaction rate of the tertiarymercaptans. Conversely, the majority of the branched mercaptansdisclosed herein are primary branched mercaptans that have minimalsteric bulk proximal to the sulfur atom. The branched mercaptanstherefore display much greater reactivity in the reaction with asulfur-containing material (e.g., elemental sulfur), when compared totertiary mercaptans. Additional advantages of the C₂₀₊ polysulfidecompositions, C₂₀₊ monosulfides compositions, and C₂₀₊ polysulfides/C₂₀₊monosulfides compositions and processes of producing same as disclosedherein can be apparent to one of skill in the art viewing thisdisclosure.

EXAMPLES

The subject matter having been generally described, the followingexamples are given as particular embodiments of the disclosure and todemonstrate the practice and advantages thereof. It is understood thatthe examples are given by way of illustration and are not intended tolimit the specification of the claims to follow in any manner.

Hydrogen sulfide (H₂S) and a feedstock comprising branched C₁₀monoolefins were reacted in the presence of various initiating agents:UV radiation, an acid catalyst, and a hydrodesulfurization (HDS)catalyst.

Various feedstocks (e.g., olefin feedstocks) were used for reacting withH₂S to produce mercaptans and/or sulfides. More specifically, olefinfeedstocks obtained from 1-hexene production processes were used asfeedstocks for reacting with H₂S to produce mercaptans. Gaschromatography (GC)-mass spectrometry (MS) (GC-MS) and nuclear magneticresonance (NMR) spectroscopy were used for analyzing the composition ofolefin feedstocks obtained from 1-hexene production processes.

The compositions comprising C₁₀ monoolefins, i.e., the feedstocksobtained from a 1-hexene production process, were analyzed by gaschromatography-mass spectrometry (GC-MS) using a 15 m×0.25 mm×0.5 μmDB-5 column and/or a 40 m×0.1 mm×0.1 μm DB-1 column to determinecomponent identities, and standard gas chromatography (GC) using a 60m×0.32 mm×1 μm DB-1 column to determine the quantity of the componentspresent in the compositions. As described previously, these compositionsare measured in area %, which is substantially similar and analogous towt. %.

Table 1 provides representative information about the composition ofsuch an olefin feedstock obtained from 1-hexene production processes toreact with H₂S to produce mercaptans—Samples #1-4 in Example 1.

TABLE 1 Chemical GC Area % Normalized % cyclohexane 2.148 octene 0.036C₈ olefins 1.17 1.24 1-octene 1.135 octane 0.146 octane 0.15 0.16ethylbenzene 1.684 3-propyl-1-heptene 14.590 C₁₀ olefins 84.16 89.11decene 0.164 4-ethyl-1-octene 13.134 5-methyl-1-nonene 32.144 decene0.647 2-butyl-1-hexene 9.960 decene 0.320 4/5 decene 9.116 1-decene4.086 decane 0.360 decane 0.36 0.38 2-ethyl-1-hexanol 1.379 dodeceneisomers 0.448 C₁₂ olefins 1.29 1.37 1-dodecene 0.842 dodecane 0.182dodecane 0.18 0.19 tetradecenes 6.710 C₁₄ olefins 6.71 7.11 tetradecane0.198 tetradecane 0.2 0.21 octadecene 0.222 C₁₈ olefins 0.22 0.232-ethylhexyl-2- 0.069 ethylhexanoate Unknowns 0.281 Total 100.000 totalolefins 94.44 99.06 Normalized to include only octane, decane, dodecane,tetradecane, and C₈, C₁₀, C₁₂, C₁₄, and C₁₈ olefins

As mentioned previously, the olefin feedstock was produced from thetrimerization of ethylene in a 1-hexene production process. As shown inTable 1, the total product content of this particular olefin feedstocksample (excluding the compounds that are not products of the 1-hexeneprocess) is 94.44 area %, and 84.16 area % of the feedstock is C₁₀olefin isomers. The C₁₀ olefins represent over 89 area % of the totalolefin content when the sample is normalized to remove the compoundsthat are not products of the 1-hexene process. Cyclohexane,ethylbenzene, and 2-ethylhexanol can be present in the olefin feedstockas residual components of the 1-hexene oligomerization process. Thestructures of C₁₀ isomers that can be present in the olefin feedstockare shown in Table 2.

TABLE 2 Decene Fraction Olefin Major UV Product Major Acid CatalystProduct 5-methyl-1- nonene 32.14% (38.19)

3-propyl-1- heptene 14.59% (17.33)

4-ethyl- 1-octene 13.13% (15.60)

2-butyl-1- hexene 9.96% (11.83)

4/5 decene 9.12% (10.83)

 

 

 

 

 

1-decene 4.09% (4.86)

In Table 2, the first column provides the name of the isomer, the GCarea % of that component in the feedstock from Table 1, and thenormalized amount of the isomer typically found in the C₁₀ fraction ofthe feedstock. Table 2 also displays the structure of the mercaptansthat are produced from the C₁₀ olefin isomers. The second column showsthe structure of the major C₁₀ olefin isomers in the feedstock; thethird column displays the structure of the major mercaptan isomersproduced by a UV-initiated reaction with H₂S; and the fourth columndisplays the structure of the major mercaptan isomers produced by acidcatalysis, such as Filtrol® 24 or Filtrol® 24X.

A sample of the olefin feedstock was fractionated (e.g., distilled) andonly the C₁₀ fraction was isolated in high purity (e.g., a purifiedfeedstock). This product was submitted for H¹ and C¹³ NMR. The NMRanalysis (in mol %) was consistent the GC-MS results. The NMR confirmedthat about 11 mol % of the total purified feedstock was vinylidene (2butyl-1-hexene isomer) and about 11 mol % of the total purifiedfeedstock was internal olefins (linear decene isomers). The nomenclaturefor the various C₁₀ isomer products is shown in Table 3.

TABLE 3 UV-initiated Acid-catalyzed C₁₀ Olefin Mercaptans Mercaptans5-methyl-1-nonene 5-methyl-1-mercapto- 5-methyl-2-mercapto- nonanenonane 3-propyl-1-heptene 3-propyl-1-mercapto- 3-propyl-2-mercapto-heptane heptane 4-ethyl-1-octene 4-ethyl-1-mercapto- 4-ethyl-mercapto-octane octane 2-butyl-1-hexene 2-butyl-1-mercapto- 5-mercapto-5-methyl-hexane nonane 4-decene 4-mercapto-decane 4-mercapto-decane5-mercapto-decane 5-mercapto-decane 5-decene 4-mercapto-decane4-mercapto-decane 5-mercapto-decane 5-mercapto-decane 1-decene1-mercapto-decane 2-mercapto-decane

Reaction of H₂S with the olefin feedstock (e.g., a feedstock comprisingbranched C₁₀ monoolefins) by UV-initiation (e.g., using UV radiation)yielded mostly primary mercaptans, since the terminal olefin andvinylidene isomers yield predominately the anti-Markovnikov product. Theminor components were secondary mercaptans from the terminal olefin anda tertiary mercaptan from the vinylidene isomer. Typically,UV-initiation of a terminal olefin produced primary mercaptans in 92-96area % range and secondary mercaptans in 4-8 area % range. The linearinternal olefin isomers present in the feedstock primarily producedsecondary mercaptan isomers. Thus, for the composition of the feedstockdisclosed herein, the distribution of mercaptans (i.e., the distributionwithin the C₁₀ fraction) in the resulting reaction product waspredominately primary mercaptans at about 80-90 area %. Secondarymercaptans were present at 10-20 area %, and tertiary mercaptans werepresent at about 0-3 area %. These ranges were calculated by NMRanalysis of the reaction product.

Reaction of H₂S with a feedstock comprising branched C₁₀ monoolefinsover an acid catalyst (such as Filtrol® 24 or Filtrol® 24X) produced asthe major product the Markovnikov product. Thus, the major mercaptanisomers comprised secondary mercaptans with some tertiary mercaptans.The relative ratio of mercaptans was estimated at 85-90 area % secondarymercaptans and 10-15 area % tertiary mercaptans.

Reaction of H₂S with a feedstock comprising branched C₁₀ monoolefins inthe presence of a hydrodesulfurization (HDS) catalyst (such as HaldorTopsoe TK-554 or TK0570) produced mercaptans generally similar indistribution to those produced by acid catalysis, which is theMarkovnikov distribution. However, the HDS catalyst also produced asignificant amount of the anti-Markovnikov product depending on theconditions used in the reaction step. Thus, under the conditions used inthis disclosure, the product produced by the HDS catalyst was a blend ofthe product produced via acid catalysis with some of the componentsproduced by the UV-initiated reaction.

As will be appreciated by one of skill in the art, and with the help ofthis disclosure, the actual composition of the resultant crude productwill ultimately depend on a number of factors including composition ofthe feedstock; the ratio of H₂S to olefin that is used to produce thethiols; the catalytic method and reaction conditions used to react theH₂S and olefin (UV-initiated, acid catalysis, or HDS catalysis) toproduce the crude product; etc. The final product (e.g., any cutsseparated from the crude to form, for example, a commercial product)will also depend on the purification step to remove lights and whether afinal product containing both mercaptan and sulfide fractions is desiredor just one of the fractions, e.g., a mercaptan fraction or a sulfidefraction, is desired.

H₂S to Olefin Molar Ratio: The H₂S to olefin molar ratio can be animportant parameter in determining the amount of mercaptan and sulfideproduced during the reaction step. This can be true regardless of thecatalytic method employed. Without wishing to be limited by theory andin general, the higher the H₂S to olefin molar ratio, the greater theamount of mercaptans that will be produced compared to the amount ofsulfides produced.

A general reaction scheme for addition of H₂S to an olefin is shown inFIG. 1, regardless of catalytic method. For a C₁₀ olefin fraction, R, R′and R″ can be H or C₁-C₈ with the total of R+R′+R″=8 carbon atoms. For1-decene, R═H and R′═H and R″=8 and can be a linear or branched alkylgroup. For the major isomers in a C₁₀ olefin fraction (e.g., a secondfeedstock as disclosed herein), 5-methyl-1-nonene: R═H and R′═H andR″=8, but the alkyl group contains branching at the third carbon atom ofthe C₈ fraction.

A sulfide fraction can be produced by further reaction of a mercaptanisomer with an olefin. The generic structures of such sulfides are shownin FIG. 1 and this fraction can consist of a variety of isomers withseveral possible combinations of sulfide structures depending on whetherthe sulfide is primary to primary, primary to secondary, primary totertiary, secondary to secondary, secondary to tertiary, or tertiary totertiary. The structures are complicated by the fact that on the twoportions of the sulfide the R, R′ and R″ value can be the same ordifferent depending on which mercaptan isomer reacts with which olefinisomer. The total number of carbon atoms of the two portions of thesulfide can also have different values for R+R′+R″, although the mostdominant combination will be where both sides each have a total sum of 8carbon atoms since the C₁₀ fraction predominates in the first feedstockand in the second feedstock.

Reaction Conditions: Three different reaction methods were used toperform the reaction of H₂S with a feedstock comprising branched C₁₀monoolefins: UV-initiation, acid catalysis, and HDS catalysis.

H₂S Removal: In laboratory experimentation, H₂S was removed using arotovapor apparatus under conditions of reduced pressure. Under theseconditions, H₂S was removed without removing significant quantities oflight compounds.

Analytical Methods: The weight percentage of thiol sulfur (wt. % SH) wasdetermined analytically by titration using iodine in water as thetitrant and methylene chloride/isopropanol as the solvent system. Suchtitration can also be done by using a silver nitrate titration method.Total sulfur was measured by X-ray using a model SLFA-20 Horibasulfur-in-oil analyzer. GC analysis of the reaction product wasperformed using an Agilent Technologies 7890A GC. A 2 m×0.25 mm×1.0 μmfilm DB-1 capillary column was used for the separation. Operatingconditions were as follows: 70° C. initial temperature, 2 min hold time,8° C./min ramp rate to 200° C. and then 15° C./min ramp rate to 300° C.and hold for 10 minutes. A 2 ml/min helium flow rate at constant flowconditions was used. A flame ionization detector was used. The injectortemperature was set at 275° C. and the detector temperature at 300° C.As described previously, these data from these compositions werereported in area %, which is substantially similar and analogous to wt.%. Olefin conversion was monitored using Raman spectroscopy with aKaiser Optical System RXN2 4-channel spectrometer. The peak centered at1640 cm⁻¹ was the vinyl olefin, while the peak centered at about 1670cm⁻¹ was the internal olefin.

Example 1

UV-initiation reactions were performed using either a 1.5 L or a 5-literUV reactor equipped with a 100 watt lamp and ballast. The two reactorsare substantially the same configuration, and the only difference inoperation is the amount of reactants added to the reactor. To 800 g ofmixed C₁₀ olefin (or 2.7 kg, if using the larger reactor), 5 g (or 16.7g) of triethyl phosphite was added and 0.2 kg (or 0.67 kg) H₂S wascharged after sealing the reactor. The reaction mixture was stirred at500-1,000 RPM. The reaction temperature was controlled with a bath setat 25° C., but the heat of reaction did reach about 40° C. The lampoperated at 1.1-1.5 amps and 28-103 volts over the course of thereaction, operating at lower amps and higher voltage as it warmed up.The reaction pressure was 220-280 psig (1,516 kPag-1,930 kPag) duringthe actual reaction time. The reaction was completed in about 30 minutesbased on the results of Raman spectroscopy but was allowed to continuefor 60 minutes to ensure completion. Table 4 shows the results of fourreactions by UV-initiation, wherein the reactions produced Samples #1,#2, #3, and #4.

TABLE 4 Sample # 1 1a 2 2a 3 3a 4 4a Olefin 800 930 930 930 Feedstockwt. H₂S wt. 200 2300 2300 2300 H2S:Olefin 1.0 10.2 10.2 10.2 Molar RatioPhosphite TEP TEP TEP TBP Phosphite wt. 5.0 1.0 1.0 1.0 wt. % 0.63 0.110.11 0.11 Phosphite Reaction Time 70.0 40.0 45.0 45.0 (minutes) % Raman97.0 98.0 97.3 97.2 Conversion wt. % SH 11.2 15.8 16.6 16.8 16.4 wt. %Total S 15.4 16.3 17.5 17.9 16.9 GC Analysis area % Lights 8.78 0.0317.07 3.61 6.96 Light 1.10 0.22 1.01 0.015 3.75 3.45 Intermediate C₁₀ SHRegion 51.85 56.84 76.04 82.45 82.38 84.14 78.29 84.02 Intermediate 4.965.71 7.91 9.04 4.23 5.75 4.26 5.82 Heavies Sulfides 33.31 37.20 7.988.50 6.03 10.10 7.05 10.15 TEP = triethyl phosphite; TBP = tributylphosphite.

Samples #1-4 were prepared using samples of an olefin feedstockcomposition comparable to that shown in Table 1. Samples #1a, #2a, #3a,and #4a were prepared by distilling the crude reaction product, Samples#1, #2, #3, and #4, respectively. The distillation process proceeded asfollows: The first 7 fractions removed from the crude reaction productwere considered to be the light fractions. This distillation step wasconsidered to be complete when the kettle temperature increased from100° C. to 121° C. and the head temperature increased from roomtemperature to 98.9° C. Cuts 8-13 were considered to be the intermediatefractions and included the C₁₀ mercaptans. These cuts were collected ata kettle temperature of 122° C. to 154° C. and a head temperature of 99°C. to 105° C. Cuts 14 and 15 were collected at kettle and headtemperatures of from 122° C. to 154° C. and 103.4° C. to 107.2° C.,respectively. These cuts and whatever remained in the kettle wereconsidered the heavies. The head temperature was allowed to increasefrom room temperature to 107.2° C. before the distillation was stopped.For a typical distillation, only the light fractions were distilled(e.g., removed) and the reaction product was what remained (e.g.,including C₁₀ mercaptans and C₂₀ sulfides) in the kettle after thelights were removed.

The relative amount of C₁₀ mercaptan isomers, intermediate mercaptans(e.g., non-C₁₀ mercaptans such as C₁₂ to C₁₆ mercaptans) and sulfideheavies (e.g., C₂₀ sulfides) depended on the ratio of H₂S to olefinduring the reaction step. Sample #1 was prepared at a 1:1 ratio of H₂Sper olefin to maximize the amount of sulfide content. Conventionalwisdom would suggest that the C₁₀ mercaptan fraction would have toostrong of an odor to be acceptable for certain applications, and thatthe sulfide fraction might have a better odor. Surprisingly andunexpectedly, after removing Sample #1 from the reactor and venting offthe residual H₂S using a rotovapor apparatus, the odor of this crudereaction product (Sample #1) was good.

FIG. 2 displays a GC trace of reactor crude Sample #1 (after removal ofresidual H₂S). FIG. 3 displays a GC trace of Sample #2 after removal oflights, designated as Sample 2a. Comparison of the GC traces in FIGS. 2and 3 indicates successful removal of the majority of the lights fromthe product stream, which include the cyclohexane, ethylbenzene,2-ethylhexanol and residual octane. Because the run (to obtain Sample#1) was performed at a low H₂S to olefin ratio, the amount of C₁₀mercaptan isomers (peaks at 3.8-6.5 minutes) accounted for 56.8 area %of the kettle product, as shown in FIG. 2. The intermediate cut (peaksat 6.5-14 minutes) included mercaptans produced from the C₁₂ to C₁₆olefins present in the olefin feedstock stream and accounted for 5.7area % of this particular sample. The heavies cut (peaks at >14 minuteretention time) included the sulfides, primarily C₁₀H₂₁—S—C₁₀H₂₁ isomersplus higher sulfides from combinations with other olefins in the mixedfeed. It is believed that any C₁₈ mercaptans that may have been producedeluted with the sulfide peaks. The amount of C₁₈ that could be presentwas estimated at about 0.2 area %. In Sample #1, the sulfide fractionaccounted for about 37.2 area % of the product composition. The amountof the intermediate fraction was primarily dependent on the amount ofC₁₄ olefin isomers that were present in the olefin feed stream. Analysisof several samples showed that this intermediate fraction ranged from4-10 area %.

FIG. 4 displays a GC trace of reactor crude Sample #3, after removal ofresidual H₂S. FIG. 5 displays a GC trace of kettle product Sample #3a,after removal of lights. FIGS. 4 and 5 compare GC results of productproduced at a 10:1 H₂S to olefin molar ratio. The observed trends aresimilar to the trends seen in FIGS. 2 and 3, and the primary differenceis in the ratio of C₁₀ mercaptan isomers to the sulfide fraction. Thisdifference is the result of increasing the ratio of H₂S to olefinfeedstock used in the reaction. The type and relative amounts of theisomers in the C₁₀ mercaptan fraction are essentially unchanged, and thecompositions of the sulfide heavies fractions are similar. What ischanged is the relative amount of the C₁₀ mercaptan fraction compared tothe sulfide heavies fraction, as in the sample with a lower H₂S:olefinsratio, there is significantly more of the sulfide fraction than themercaptan fraction. This result is not altogether unexpected, althoughfurther experimentation would allow one of skill in the art to optimizethe H₂S to olefins ratio to obtain a specific ratio of mercaptans tosulfides.

The main difference between Sample #3a and Sample #1a is the relativeamounts of C₁₀ mercaptan isomers, intermediate mercaptans, and sulfides.As expected, when the reaction was performed at a higher molar ratio ofH₂S per olefin, the resulting reaction product contained a greateramount of C₁₀ mercaptan isomers (84.1 area % vs. 56.8 area %) and muchless sulfide (10.1 area % vs. 37.2 area %). The removal of lights wasdone using a simple lab distillation unit, wherein the distillationcolumn was 12″ long and 1″ in diameter and was packed with a stainlesssteel sponge. Distillations were performed in batch mode at 9-10 torrvacuum pressure and an overhead temperature of about 100° C.−103° C. anda kettle temperature of about 125° C.−150° C. The lights were collectedoverhead while trying to minimize the amount of C₁₀ mercaptan isomersthat were lost with this overhead fraction.

The composition of the UV-produced product can be described in broadterms as follows: a feedstock was reacted with H₂S; removal of H₂S afterthe reaction yielded a crude reaction product. Subsequent removal of thelights fraction to yields a kettle product, which can be used “as is”(e.g., a composition comprising both mercaptans and sulfides) or can befurther separated into one or more products or cuts corresponding to adesired compound or combination of compounds (e.g., a C₁₀ mercaptanfraction, an intermediate mercaptan fraction, and/or a heavy/sulfidefraction). In broad terms, the product consists of three generalfractions as produced from the kettle product after removal of theunwanted lights fraction. The C₁₀ mercaptan fraction comprised from50-100 wt. % of the kettle product. The mercaptan functionality of theC₁₀ mercaptan fraction was 80-90% primary mercaptan, 5-18% secondarymercaptan and 0-3% tertiary mercaptan. This was the fraction that elutedin the 3.8-6.5 minute range under the GC conditions used. Theintermediate fraction, which eluted in the 6.5-14 minute region, waspredominately mercaptan isomers in the C₁₂ to C₁₈ range with adistribution of functionality that can be similar to that for the C₁₀isomer fraction. The intermediate fraction comprised from 0 to 12 area %of the kettle product. The heavy fraction (>14 minute retention time)consisted essentially of sulfides, primarily of formula C₁₀H₂₁—S—C₁₀H₂₁isomers, as well as sulfides from C₁₂, C₁₄, C₁₆ or C₁₈ olefins andmercaptans or the asymmetric sulfides produced from the variouscombinations. These sulfide components comprised from 0-70 area % of thekettle product, depending on the reaction conditions used.

Example 2

Acid Catalysis produced a different distribution of isomer products thanthose produced by UV-initiation reaction of H₂S and the olefin feedstockcomprising branched C₁₀ monoolefins.

The product produced via the acid catalyzed addition of H₂S to thefeedstock comprising branched C₁₀ monoolefins was prepared in acontinuous flow reactor over Filtrol® 24 acid catalyst. The reactorcontained 43.22 g of catalyst and the WHSV (weight hourly spacevelocity) was maintained at 1.0 grams of olefin per gram of catalyst perhour. The H₂S to olefin molar ratio ranged from 10:1 to 1:1. Thereaction temperature was between 120° C. to 220° C., and the reactorpressure was 450-460 psig (3,100 kPag-3,200 kPag). Optimum results,based on conversion and maximum C₁₀ mercaptan, were in the 180-200° C.range and an H₂S to olefin molar ratio of 5:1. A decrease in the H₂S toolefin ratio resulted in a decrease in the C₁₀ mercaptan fraction and acorresponding increase in the sulfide fraction. The run data for theacid catalyzed reactions are shown in Table 5.

TABLE 5 Sample # 5 6 7 8 9 10 11 12 13 14 15 16 17 18 Mid Temp 123 145167 186 202 221 184 185 202 165 182 201 182 182 Actual Btm Temp Set 122142 162 182 202 222 185 185 205 165 185 205 185 185 Btm Temp 120 141 160179 198 219 182 182 201 163 181 201 181 182 Actual Average Actual 121142 163 182 200 221 183 184 202 163 182 202 182 182 Temp GC Analysisarea % Lights 4.34 4.24 4.16 3.95 4.24 5.85 3.85 3.88 4.08 3.97 4.043.99 4.02 3.94 Olefin Region 58.03 39.66 18.56 11.93 12.70 22.22 9.669.79 11.35 12.90 13.45 17.34 19.75 15.86 Octyl SH 0.03 0.57 1.24 0.011.67 1.48 1.19 1.19 1.44 1.06 1.12 1.06 0.83 0.92 Other Lights 0.51 0.180.13 0.00 0.73 1.26 0.40 0.33 0.54 0.00 0.01 0.02 0.24 0.21 C₁₀Mercaptan 15.64 36.81 52.84 61.44 56.82 49.41 56.57 57.48 55.80 61.9758.38 50.79 42.78 48.51 Region Intermediate 7.80 11.67 11.07 6.78 6.246.71 6.32 6.27 6.88 6.86 7.05 6.67 6.65 6.57 Heavies Sulfides 13.65 6.8812.00 15.88 17.59 13.08 22.01 21.06 19.91 13.24 15.95 20.13 25.73 24.00Raman Olefin 31.0% 56.2% 81.5% 91.0% 92.5% 89.8% 93.2% 92.2% 91.9% 86.4%85.4% 81.7% 76.2% 78.4% Conversion mol %

The best olefin conversions were in the 88-92 area % range. The C₁₀mercaptan fraction accounted for 50-60 area % of the crude productweight, while the sulfide fraction ranged from 15-25 area % of the crudeproduct weight.

Acid catalysis produced the Markovnikov product. The vinyl components ofthe feedstock comprising branched C₁₀ monoolefins produced secondarymercaptans. The internal olefin components produced secondarymercaptans, while the vinylidene components produced tertiarymercaptans. Thus, the composition of the C₁₀ mercaptan fraction isomerswas different when compared to the composition of the product obtainedby UV-initiation. For example, the 5-methyl-1-nonene isomer produced5-methyl-2-mercapto-nonane by acid catalysis; and5-methyl-1-mercapto-nonane was the major product produced byUV-initiation, with a minor amount of the 2-mercapto isomer as aby-product. The 2-butyl-1-hexene isomer produced5-methyl-5-mercapto-nonane by acid catalysis; while UV-initiationproduced 2-butyl-1-mercapto-hexane. Comparative GC traces of the productproduced by acid catalysis and that produced by UV-initiation are shownin FIG. 6 and FIG. 7. FIG. 6 shows a comparison of crude product (e.g.,only H₂S removed) by UV-initiation and acid catalysis routes, and FIG. 7compares the C₁₀ mercaptan fraction produced by the UV-initiation andacid catalysis routes.

The comparative GC traces in FIG. 6 and FIG. 7 demonstrate thatdifferent isomer distributions can be obtained depending on how thereaction of the feedstock comprising branched C₁₀ monoolefins and H₂S isinitiated. One would expect that the tertiary and secondary mercaptanswould elute more quickly than primary mercaptans. One would alsoanticipate that more branching and proximity of the branching to themercaptan would also cause those isomers to elute more quickly. The peakat 6.01 minutes was clearly n-decyl mercaptan and was expected to be thelast of the C₁₀ mercaptans to elute in this fraction.

As with the product produced by UV-initiation, the product obtained byacid catalysis consisted of three general fractions as produced as akettle product after removal of the unwanted lights fraction. The C₁₀mercaptan fraction comprised from 50-100 area % of the crude kettlecomposition. The mercaptan functionality of the C₁₀ fraction was 85-95area % secondary mercaptan and the remainder tertiary mercaptan. Theseisomers eluted in the 3.1-6.5 minute range under the utilized GCconditions.

The intermediate fraction consisted of those mercaptan peaks in the6.5-14 minute range. However, the functionality of the mercaptans wassecondary and tertiary C₁₂ to C₁₈ mercaptans. The intermediate fractioncomprised 5-15 area % of the total kettle composition.

The sulfide fraction comprised 0-70 area % of the composition of thekettle product, depending on the specific reaction conditions. Thefraction consisted of sulfides primarily of formula C₁₀H₂₁—S—C₁₀H₂₁.However, the isomer identity was different than that for the productproduced by UV-initiation. The acid produced sulfide product was basedon secondary and tertiary mercaptans rather than predominately primarymercaptans as in the UV-initiated produced product.

Example 3

HDS Catalysis produced mercaptans that were primarily similar indistribution to those produced by acid catalysis, which is theMarkovnikov distribution. However, there was a tendency to also producesome of the anti-Markovnikov distribution depending on the specificconditions utilized in the reaction step. Thus the product produced bythe HDS catalyst appeared to be a blend of product produced primarilyvia acid catalysis with some of the components of the UV-initiatedreaction.

The HDS reaction conditions were as follows: WHSV was varied from 0.75to 2 grams of olefin per gram of catalyst per hour; the molar ratio ofH₂S per olefin was varied from 2:1 to 10:1; the average reactiontemperature was 180° C. to 220° C. The catalyst used was cobaltmolybdenum on alumina, examples being to Haldor Topsoe TK-554, TK-570,or similar. Olefin conversion, as determined by Raman spectroscopy, wasin the 88-97 mol % range. The HDS test runs were performed using thefeedstock comprising branched C₁₀ monoolefins comparable to thecomposition as outlined in Table 1 are shown in Table 6 and Table 7.

TABLE 6 Sample # 19 20 21 22 23 24 25 26 27 Ratio 10 10 10 10 10 5 2 5 5H₂S/Olefin Olefin Rate 31.2 31 31.4 31.1 30.4 31.1 30.8 31.2 31.4 (g/hr)H₂S Rate 74.8 74.2 74.7 75 74.2 36.9 14.4 36.8 37 (g/hr) WHSV 0.75 0.750.75 0.75 0.75 0.75 0.75 0.75 0.75 Average 204 205 204 223 202 203 203203 203 Actual Temp GC Analysis area % Lights 6.97 5.33 5.16 4.02 4.974.98 4.77 4.59 4.83 Olefin 6.22 7.06 8.93 9.89 8.50 7.35 6.53 7.01 7.28Region Octyl SH 1.01 1.60 2.07 1.71 1.75 2.07 2.05 2.04 2.16 C₁₀ 51.4360.92 75.05 59.89 73.44 80.77 79.73 78.53 80.92 Mercaptan RegionIntermediate 3.71 4.03 3.86 4.73 4.02 3.78 3.79 4.59 3.97 heaviesSulfides 30.62 21.05 4.93 19.74 7.32 1.06 3.13 3.24 0.83 Raman 96.8%96.9% 96.1% 94.2% 96.6% 97.5% 97.9% 97.7% 97.2% Olefin Conv. mol %Notes: About 3-4% of olefin region is saturates; lights are primarilycyclohexane, octane, and ethylbenzene

TABLE 7 Sample # 28 29 30 31 32 33 34 35 36 37 38 39 Ratio 5 5 2 5 5 5 55 5 5 5 5 H₂S/Olefin Olefin Rate 40.8 41.7 41.6 62.7 61.7 60.7 81.8 82.461.7 62.7 41.8 41.2 (g/hr) H₂S Rate 50.1 49.6 20 74.7 74.5 75 99.5 9974.4 74.7 49.5 50.1 (g/hr) WHSV 1 1 1 1.50 1.50 1.50 2.00 2.00 1.50 1.501.00 1.00 Average 203 203 204 203 203 212 203 218 183 183 181 191 ActualTemp GC Analysis area % Lights 4.02 4.47 4.24 4.07 4.04 3.61 3.51 3.673.40 3.68 3.45 3.65 Olefin 7.21 8.65 7.84 11.07 11.73 10.01 13.25 14.8216.38 18.94 13.61 10.49 Region Octyl SH 1.58 1.91 1.71 1.63 1.67 1.791.42 1.50 1.12 1.21 1.19 1.48 C₁₀ 66.44 77.68 77.74 73.33 73.27 63.4959.35 65.04 58.50 64.23 65.26 71.64 Mercaptan Region Intermediate 5.635.21 5.45 5.64 5.33 7.60 7.76 8.04 8.31 7.34 8.27 8.21 Heavies Sulfides15.12 2.07 3.02 4.26 3.95 13.40 14.58 6.81 12.15 4.45 8.08 4.41 Raman96.6% 96.6% 97.0% 94.9% 93.9% 94.4% 91.1% 90.4% 87.3% 87.0% 90.9% 94.9%Olefin Conv. mol %

As can be observed from Tables 6 and 7, the trends for sulfideproduction were less consistent, possibly because the continuous reactorwas run at steady state conditions for about 4-5 hours, shut down, andrestarted the next day. Further, it appeared that the initial sampleeach day was initially higher in sulfide content than anticipated andthen declined. It appears that under similar conditions of WHSV, ratioand temperature, the HDS catalyzed reaction produces more C₁₀ mercaptanfraction and less sulfide fraction than the acid catalyzed reaction. Itis expected that the results varied compared to what would be obtainedif the reactor was operated continuously at steady state conditions forseveral weeks.

A typical GC trace of reactor crude produced from the HDS catalyzedreaction of H₂S and branched C10 monoolefins is shown in FIG. 8.Comparison of the C₁₀ fraction (3.5 to 6 minute retention time) of theHDS reaction product, as shown in FIG. 8, with the same reaction productfor both the acid catalyzed and UV-initiated processes as shown in FIG.6 or FIG. 7, shows that the HDS product was a blend of the acidcatalyzed and UV-initiated products.

Example 4

Purification of Crude Decyl Mercaptan. Purification was performed onsome the crude product samples to remove the lights fraction, whichconsisted of residual H₂S, cyclohexane, ethylbenzene, octane, octene,2-ethylhexanol and as much of the n-octylmercaptan as possible, i.e.,all C⁹⁻. Purification was performed in a conventional laboratorydistillation column. Removing the light fraction, especially then-octylmercaptan, can result in the loss of some C₁₀ mercaptan isomersto the overhead distillate product. It is believed that acommercial-scale operation can minimize the loss of C₁₀ mercaptans bycontrolling operating parameters including the number of distillationcolumns used, the number of theoretical trays in the column(s), the rateof reflux and take-off, and whether the distillation is done incontinuous or batch mode. These parameters can readily be determinedwith research, allowing one of reasonable skill in the art to scale upand optimize the distillation process. It is within the scope of thisdisclosure that operating a continuous mode distillation system usingtwo columns can provide satisfactory separation. For example, operatinga the first column at an overhead temperature of 80° C. to 85° C. at 9torr and a second column at about 95° C.−97° C. would provide asatisfactory separation.

The distillation column used in the lab was 1″×12″ packed with stainlesssteel sponge. As stated earlier, it is believed that the separation wasnot as good as desired, and significant C₁₀ mercaptan was removedoverhead, even with the initial cut. A distillation run at 9 torr and areflux to take-off ratio of 18:3 required the removal of 12.5 area % ofthe crude overhead to reach a level of <0.1 area % lights in the kettleproduct. According to the GC analysis of the crude, only 8.1 area % ofthe crude product was lights that needed to be removed overhead. Thekettle temperature was in the 100° C.-115° C. range at 9 torr. Inanother distillation batch, 8.8 area % of the crude was taken overhead,while the lights composed only 4.0 area % of the crude. In several otherbatches, nearly 20 area % of the crude was lost overhead.

For simulation of the distillation, the nearest boiling point impuritiesare the ethylbenzene, 2-ethylhexanol and n-octylmercaptan. The amount ofthese impurities that are present will determine how many theoreticaltrays are be needed, as well as the best pressure and temperatureprofile to optimize yield and keep the level of the n-octylmercaptan toas low a value as feasible.

Prophetic Example 5

Olefin Feedstock Purification. A feedstock comprising branched C₁₀monoolefins produced in a 1-hexene process can be purified (e.g.,distilled), for improved olefin reactivity and resulting mercaptanpurity. The lights up to 1-octene can be removed and the C₁₀ olefinisomers taken overhead to high purity (>98%). This high purity C₁₀monoolefin cut would then be free of the C₁₂ to C₁₈ olefins. The highpurity C₁₀ olefin can then be reacted with H₂S to produce the mercaptanproducts. The reaction conditions would be identical for the high purityC₁₀ olefin stream (e.g., second feedstock) as already indicated for thefeedstock comprising branched C₁₀ monoolefins produced in a 1-hexeneprocess used as received (e.g., first feedstock). The major differencewill be in the composition of the crude stream and product stream. Forthe second feedstock, the crude product would consist of any residualH₂S and unreacted C₁₀ olefin, the C₁₀ mercaptan isomers and theC₁₀H₂₁—S—C₁₀H₂₁ fraction. Once the lights are removed, the product willcontain the C₁₀ mercaptan isomers and the C₂₀-sulfide, but will notcontain any of the intermediate mercaptans and asymmetric sulfidecomponents, which come from reaction of C₁₀ mercaptan with the othernon-C₁₀ olefins. The mercaptan functionality for the various routes willbe the same as already indicated.

Example 6

UV-initiation reactions of NEODENE 1112 IO higher olefins were performedin a 1.5 L UV reactor equipped with a 100 watt lamp and ballast. To203.9 g of the NEODENE 1112 IO higher olefins, 650 g of H₂S was chargedafter sealing the reactor. The reaction mixture was stirred at 500-1,000RPM. The reaction temperature was controlled with a bath set at 25° C.,but the heat of reaction did reach about 40° C. The lamp operated at1.0-1.7 amps and 25-112 volts over the course of the reaction, operatingat lower amps and higher voltages as it warmed up. The reaction pressurevaried from 315-350 psig (2,172 kPag-2,413 kPag) during the actualreaction time. The reaction was typically completed in approximately 30minutes as monitored by RAMAN spectroscopy analysis but was allowed tocontinue for 90 min to ensure completion. The H₂S was vented and thereaction mixture was purged three times with nitrogen to remove excessH₂S to the extent possible. Additional H₂S removal was conducted using arotary evaporator. The conversion was measured as 98% by gaschromatography (GC) with the constituent components determined to be 41wt. % C₁₁ mercaptan, 41 wt. % C₁₂ mercaptan, ˜4 wt. % sulfides and 14wt. % unreacted olefin. Distillation of the C₁₁₊ mercaptans crudecomposition sample was performed at a kettle temperature of 137° C. andwas complete when the head temperature reached ˜120° C. at 9 mm Hgvacuum to give a kettle product with low perceived odor. The productmixture or kettle product (containing the intermediate and heavyfractions recovered from the C₁₁₊ mercaptans crude composition) wasanalyzed by GC and determined to be 40.2 wt. % C₁₁ mercaptan, 53 wt. %C₁₂ mercaptan, 7 wt. % sulfides and 0.3 wt. % light mercaptan/unreactedolefin. Mercaptan sulfur was determined using titration as well anddetermined to be 16 wt. % vs. a GC calculation of 15.4 wt. %. Totalsulfur was determined by X-ray to be 16.8 wt. % versus a GC calculationof ˜15.8 wt. %.

Example 7

UV-initiation reactions of NEODENE 1314 IO higher olefins were performedin a 1.5 L UV reactor equipped with a 100 watt lamp and ballast. The UVprepared sample was prepared in the 1.5 L UV reactor equipped with a 100watt lamp and ballast. To 229.6 g of the NEODENE 1314 IO higher olefins,650 g of H₂S was charged after sealing the reactor. The reaction mixturewas stirred at 500-1,000 RPM. The reaction temperature was controlledwith a bath set at 25° C., but the heat of reaction did reach about 40°C. The lamp operated at 1.0-1.5 amps and 25-110 volts over the course ofthe reaction, operating at lower amps and higher voltages as it warmedup. The reaction pressure varied from 305-340 psig (2,103 kPag-2,344kPag) during the actual reaction time. The reaction was typicallycompleted in approximately 30 minutes as monitored by RAMAN spectroscopyanalysis but was allowed to continue for 70 min to ensure completion.The H₂S was vented and the reaction mixture purged three times withnitrogen to remove excess H₂S to the extent possible. Additional H₂Sremoval was conducted using a rotary evaporator. The conversion wasmeasured as 79% by GC with the constituent components determined to be38 wt. % C₁₃ mercaptan, 39.4 wt. % C₁₄ mercaptan, ˜2 wt. % sulfides and21 wt. % unreacted olefin. Distillation of the C₁₁₊ mercaptans crudecomposition sample was performed at a kettle temperature of 149° C. andwas complete when the head temperature reached ˜100° C. at 3 mm Hgvacuum to give a kettle product with low perceived odor. The productmixture or kettle product (containing the intermediate and heavyfractions recovered from the C₁₁₊ mercaptans crude composition) wasanalyzed by GC and determined to be 45 wt. % C₁₃ mercaptan, 46 wt. % C₁₄mercaptan, 6 wt. % sulfides and 3 wt. % light mercaptan/unreactedolefin. Mercaptan sulfur was determined using titration as well anddetermined to be 14 wt. % vs. a GC calculation of 13.1 wt. %. Totalsulfur was determined by X-ray to be 14.6 wt. % versus a GC calculationof ˜13.5 wt. %.

Example 8

UV-initiation reactions of NEODENE 14/16 higher olefins were performedin a 1.5 L UV reactor equipped with a 100 watt lamp and ballast. To217.6 g of the NEODENE 14/16 higher olefins, 650 g of H₂S was chargedafter sealing the reactor. The reaction mixture was stirred at 500-1,000RPM. The reaction temperature was controlled with a bath set at 25° C.,but the heat of reaction did reach about 40° C. The lamp operated at1.0-1.6 amps and 25-120 volts over the course of the reaction, operatingat lower amps and higher voltages as it warmed up. The reaction pressurevaried from 310-340 psig (2,137 kPag-2,344 kPag) during the actualreaction time. The reaction was typically completed in approximately 30minutes as monitored by RAMAN analysis but was allowed to continue for55 min to ensure completion. The H₂S was vented and the reaction mixturepurged three times with nitrogen to remove excess H₂S to the extentpossible. Additional H₂S removal was conducted using a rotaryevaporator. The conversion was measured as 93% by GC with theconstituent components determined to be 57.4 wt. % C₁₄ mercaptan, 30.1wt. % C₁₆ mercaptan, ˜6 wt. % sulfides and 7 wt. % unreacted olefin.Distillation of the C₁₁₊ mercaptans crude composition sample wasperformed at a kettle temperature of 170° C. and was complete when thehead temperature reached ˜40° C. at 0 mm Hg vacuum to give a kettleproduct with low perceived odor. The product mixture or kettle product(containing the intermediate and heavy fractions recovered from the C₁₁₊mercaptans crude composition) was analyzed by GC and determined to be 57wt. % C₁₄ mercaptan, 30 wt. % C₁₆ mercaptan, 13.4 wt. % sulfides and 0wt. % light mercaptan/unreacted olefin. Mercaptan sulfur was determinedusing titration as well and determined to be 12 wt. % vs. a GCcalculation of 11.6 wt. %. Total sulfur was determined by X-ray to be12.9 wt. % versus a GC calculation of ˜12.5 wt. %.

Example 9

To produce a C₂₀ polysulfide composition a feedstock comprising branchedC₁₀ mercaptans was mixed with a catalyst then heated and reacted withelemental sulfur.

A 2 L Resin flask was equipped with an overhead stirrer, a heatingmantle controlled by an internal thermocouple, a condenser, and a N₂sparge. A quantity of 125.25 grams of branched C₁₀ mercaptans was addedto the reaction flask followed by 0.08 grams of Tergitol® 15-S-10 and0.06 grams of aqueous sodium hydroxide solution, 50% (w/w). The mixtureof components was placed under an atmosphere of N₂ and heated toapproximately 100° C. with continuous stirring that was maintainedthroughout the entire experimental procedure. To the heated mixture wasadded 17 grams of sulfur in several portions over approximately 30minutes. The rate of sulfur addition was monitored and managed tomaintain the rate of H₂S gas evolution at a controllable level. Afterthe addition of sulfur was complete, N₂ was sparged into the mixture toremove H₂S. After approximately 30 minutes the temperature was slowlyraised (over a period of about 45 min) to 120° C. while N₂ spargingcontinued. The reaction mixture was held at the temperature of 120° C.for approximately 3 h. Then, the mixture was cooled and filtered. Gaschromatography showed conversion of the mercaptan as displayed in FIGS.9 and 10.

ADDITIONAL DISCLOSURE

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an embodiment ofthe present disclosure. Thus, the claims are a further description andare an addition to the detailed description of the present disclosure.The disclosures of all patents, patent applications, and publicationscited herein are hereby incorporated by reference.

A first aspect which is a composition comprising polysulfides, whereinat least about 50 wt. % of the polysulfides are branched C₂₀ to C₆₀polysulfides represented by general formula R¹⁵S¹—[S]_(n)—S²R¹⁶ whereinR¹⁵ and R¹⁶ are each independently a branched C₁₀ to C₃₀ alkyl group andwherein n is an integer from 1 to 10.

A second aspect which is the composition of the first aspect furthercomprising monosulfides represented by general formula R¹⁷—S—R¹⁸,wherein R¹⁷ and R¹⁸ are each independently a branched C₁₀ to C₃₀ alkylgroup represented by Structure K30-A, Structure K30-B, Structure K30-C,Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, orStructure K30-H, wherein * designates an attachment point with a sulfuratom of the monosulfide; and R⁹ is a C₁ to C₂₁ alkyl group.

A third aspect which is the composition of the first or second aspectwherein the branched C₁₀ to C₃₀ alkyl group is represented by StructureK30-A, Structure K30-B, Structure K30-C, Structure K30-D, StructureK30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an S¹ atom of an R¹⁵S¹ group or an S² atom of an R¹⁶S² group,and R⁹ is a C₁ to C₂₁ alkyl group.

A fourth aspect which is the composition of any of the first threeaspects wherein the branched C₁₀ to C₃₀ alkyl group is represented byStructure K-A, Structure K-B, Structure K-C, Structure K-D, StructureK-E, Structure K-F, Structure K-G, or Structure K-H, wherein *designates an S¹ atom of an R¹⁵S¹ group or an S² atom of an R¹⁶S² group.

A fifth aspect which is a process of producing a polysulfides crudeproduct comprising one or more branched C₂₀ to C₆₀ polysulfidescomprising: (A) reacting a feedstock comprising one or more branched C₁₀to C₃₀ mercaptans and sulfur in the presence of a catalyst and (B)collecting the polysulfides crude product.

A sixth aspect which is the process of the fifth aspect wherein the oneor more branched C₁₀ to C₃₀ mercaptans are represented by Structure A-1,Structure B-1, Structure C-1, Structure D-1, Structure E-1, StructureF-1, Structure G-1, Structure H-1, or combinations thereof, wherein R⁹is a C₁ to C₂₁ alkyl group.

A seventh aspect which is the process of the fifth or sixth aspectwherein the one or more branched C₂₀ to C₆₀ polysulfides arepolysulfides represented by general formula R¹⁵S¹—[S]_(n)—S²R¹⁶, whereinn is an integer from 1 to 10; R¹⁵ and R¹⁶ are each independently abranched C₁₀ to C₃₀ alkyl group represented by Structure K30-A,Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E,Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an S¹ atom of an R¹⁵S¹ group or an S² atom of an R¹⁶S² group;and R⁹ is a C₁ to C₂₁ alkyl group.

An eighth aspect which is the process of any of the fifth throughseventh aspects wherein (A) reacting further comprises: (a) contactingthe one or more branched C₁₀ to C₃₀ mercaptans and the catalyst to forma mixture wherein a weight ratio of catalyst to mercaptans is in a rangeof from about 0.005:1 to about 0.013:1; (b) heating the mixture to atemperature in a range of from about 60° C. to about 85° C.; (c) heatingthe mixture to a temperature in a range of from about 90° C. to about150° C.; and (d) cooling the mixture to a temperature in a range of fromabout 65° C. to about 85° C.

A ninth aspect which is the process of any of the fifth through eighthaspects wherein (B) collecting the crude product comprises: (e) coolingthe mixture to a temperature in a range of from about 20° C. to about35° C.; and (f) filtering the polysulfides crude product.

A tenth aspect which is the process of any of the fifth through ninthaspects wherein during step (b): (i) the mixture is contacted withelemental sulfur wherein an equivalent molar ratio of sulfur tomercaptans is in a range of from about 0.07:1 to about 1.2:1; and (ii)the mixture is agitated for a time period of from about 2 hours to about6 hours.

An eleventh aspect which is the process of any of the fifth throughtenth aspects wherein during step (c): (i) the mixture is agitated for atime period of from about 2 hours to about 4 hours; and (ii) the mixtureis sparged with an inert gas for a time period of from about 0.5 hour toabout 4 hours.

A twelfth aspect which is the process of any of the fifth througheleventh aspects wherein during step (d): (i) an epoxide is added to themixture over a time period of from about 10 min to about 2 hours whereinan equivalent molar ratio of epoxide to mercaptans is in a range of fromabout 0.05:1 to about 0.1:1; (ii) the mixture is agitated for a timeperiod of from about 1 hour to about 4 hours; and (iii) the mixture issparged with an inert gas for a time period of from about 0.5 hour toabout 4 hours.

A thirteenth aspect which is the process of any of the fifth throughtwelfth aspects wherein the epoxide comprises ethylene oxide, propyleneoxide, or a combination thereof.

A fourteenth aspect which is the process of any of the fifth throughthirteenth aspects wherein the catalyst comprises: (i) a surfactant and(ii) a Group 1 or Group 2 metal hydroxide, wherein a weight ratio of (i)to (ii) is in a range of from about 25:1 to about 40:1.

A fifteenth aspect which is the process of any of the fifth throughfourteenth aspects wherein prior to contacting the catalyst with the oneor more branched C₁₀ to C₃₀ mercaptans, (i) and (ii) are combined andheated to a temperature in a range of from about 60° C. to about 100° C.and the temperature is maintained for a time period of from about 30 minto about 2 hours.

A sixteenth aspect which is the process of the fourteenth or fifteenthaspects wherein the surfactant comprises a nonionic surfactant.

A seventeenth aspect which is the process of any of the fourteenththrough sixteenth aspects wherein the surfactant comprises apolyethoxylated alcohol, a polyethoxylated mercaptan, or a combinationthereof.

An eighteenth aspect which is the process of any of the fourteenththrough seventeenth aspects wherein the Group 1 or Group 2 metalhydroxide is a solid or is dissolved in an aqueous solution.

A nineteenth aspect which is the process of any of the fourteenththrough eighteenth aspects wherein the Group 1 or Group 2 metalhydroxide is sodium hydroxide.

A twentieth aspect which is the process of any of the fifth throughnineteenth aspects wherein (A) reacting further comprises: (a)contacting the one or more branched C₁₀ to C₃₀ mercaptans and thecatalyst to form a mixture wherein a weight ratio of catalyst tomercaptans is in a range of from about 0.005:1 to about 0.013:1; (b)contacting the mixture with elemental sulfur wherein an equivalent molarratio of sulfur to mercaptans is in a range of from about 0.07:1 toabout 1.2:1; (c) heating the mixture to a temperature in a range of fromabout 60° C. to about 85° C. and maintaining the temperature while themixture is agitated for a time period of from about 2 hours to about 6hours; (d) heating the mixture to a temperature in a range of from about90° C. to about 150° C. and maintaining the temperature while themixture is agitated for a time period of from about 2 hours to about 4hours and subsequently sparged with an inert gas for a time period offrom about 0.5 hour to about 4 hours; and (e) cooling the mixture to atemperature in a range of from about 65° C. to about 85° C. andmaintaining the temperature while: (i) an epoxide is added to themixture over a time period of from about 10 min to about 2 hours whereinan equivalent molar ratio of epoxide to mercaptans is in a range of fromabout 0.05:1 to about 0.1:1; (ii) the mixture is agitated for a timeperiod for a time period of from about 1 hour to about 4 hours; and(iii) the mixture is sparged with an inert gas for a time period of fromabout 0.5 hour to about 4 hours.

A twenty-first aspect which is the process of any of the fifth throughtwentieth aspects wherein after cooling the mixture (d), the processfurther comprises: (e) adding a decolorizing agent to the mixture,wherein a weight ratio of decolorizing agent to mercaptans is in a rangeof from about 0.01:1 to about 0.02:1; (f) heating the mixture to atemperature in a range of from about 40° C. to about 60° C., andmaintaining the temperature for a time period of from about 30 min toabout 2 hours; (g) cooling the mixture to a temperature in a range offrom about 20° C. to about 35° C.; and (h) collecting the polysulfidescrude product.

A twenty-second aspect which is a process of producing one or morebranched C₂₀ to C₆₀ polysulfides comprising: (a) reacting hydrogensulfide (H₂S) and a feedstock comprising one or more branched C₁₀ to C₃₀olefins in the presence of an initiating agent to produce a branchedC₁₀₊ mercaptans crude composition; (b) recovering an intermediatereaction product comprising one or more branched C₁₀ to C₃₀ mercaptansfrom the branched C₁₀₊ mercaptans crude composition; (c) reacting sulfurand the intermediate reaction product comprising one or more branchedC₁₀ to C₃₀ mercaptans in the presence of a catalyst; and (d) collectinga C₂₀₊ polysulfides crude product comprising the one or more branchedC₂₀ to C₆₀ polysulfides.

A twenty-third aspect which is the process of the twenty-second aspectwherein the one or more branched C₁₀ to C₃₀ olefins are represented byStructure I-1, Structure J-1, Structure K-1, Structure L-1, orcombinations thereof, wherein R⁹ is a C₁ to C₂₁ alkyl group.

A twenty-fourth aspect which is the process of the twenty-second or thetwenty-third aspect wherein the one or more branched C₁₀ to C₃₀mercaptans are represented by Structure A-1, Structure B-1, StructureC-1, Structure D-1, Structure E-1, Structure F-1, Structure G-1,Structure H-1, or combinations thereof, wherein R⁹ is a C₁ to C₂₁ alkylgroup.

A twenty-fifth aspect which is the process of any of the twenty-secondthrough twenty-fourth aspects wherein the one or more branched C₂₀ toC₆₀ polysulfides are represented by general formula R¹⁵S¹—[S]_(n)—S²R¹⁶,wherein n is an integer from 1 to 10; and R¹⁵ and R¹⁶ are eachindependently a branched C₁₀ to C₃₀ alkyl group represented by StructureK30-A, Structure K30-B, Structure K30-C, Structure K30-D, StructureK30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an S¹ atom of an R¹⁵S¹ group or an S² atom of an R¹⁶S² group;and R⁹ is a C₁ to C₂₁ alkyl group.

A twenty-sixth aspect which is the process of any of the twenty-secondthrough twenty-fifth aspects wherein the one or more branched C₁₀ to C₃₀olefins comprise 5-methyl-1-nonene (represented by Structure I),3-propyl-1-heptene (represented by Structure J), 4-ethyl-1-octene(represented by Structure K), 2-butyl-1-hexene (represented by StructureL), or combinations thereof:

A twenty-seventh aspect which is the process of any of the twenty-secondthrough twenty-sixth aspects wherein the one or more branched C₁₀ to C₃₀mercaptans comprise 5-methyl-1-mercapto-nonane (represented by StructureA), 3-propyl-1-mercapto-heptane (represented by Structure B),4-ethyl-1-mercapto-octane (represented by Structure C),2-butyl-1-mercapto-hexane (represented by Structure D),5-methyl-2-mercapto-nonane (represented by Structure E),3-propyl-2-mercapto-heptane (represented by Structure F),4-ethyl-2-mercapto-octane (represented by Structure G),5-methyl-5-mercapto-nonane (represented by Structure H), or combinationsthereof:

A twenty-eighth aspect which is the process of any of the twenty-secondthrough twenty-seventh aspects wherein the one or more branched C₂₀ toC₆₀ polysulfides are polysulfides represented by general formulaR¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integer from 1 to 10; and R¹⁵ andR¹⁶ are each independently a branched C₁₀ alkyl group by Structure K-A,Structure K-B, Structure K-C, Structure K-D, Structure K-E, StructureK-F, Structure K-G, or Structure K-H, wherein * designates an S¹ atom ofan R¹⁵S¹ group or an S² atom of an R¹⁶S² group.

A twenty-ninth aspect which is a composition comprising: (A) at leastabout 25 wt. % branched C₂₀ to C₆₀ polysulfides represented by generalformula R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integer from 1 to 10,wherein R¹⁵ and R¹⁶ are each independently a branched C₁₀ to C₃₀ alkylgroup represented by Structure K30-A, Structure K30-B, Structure K30-C,Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, orStructure K30-H, wherein * designates an S¹ atom of an R¹⁵S¹ group or anS² atom of an R¹⁶S² group, and wherein R⁹ is a C₁ to C₂₁ alkyl group;and (B) at least about 5 wt. % branched C₂₀ to C₆₀ monosulfidesrepresented by general formula R¹⁷—S—R¹⁸, wherein R¹⁷ and R¹⁸ are eachindependently a branched C₁₀ to C₃₀ alkyl group represented by StructureK30-A, Structure K30-B, Structure K30-C, Structure K30-D, StructureK30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an attachment point with a sulfur atom of the branched C₂₀ toC₆₀ monosulfide, and wherein R⁹ is a C₁ to C₂₁ alkyl group.

A thirtieth aspect which is a composition comprising: (A) from at leastabout 50 wt. % to at least about 90 wt. % polysulfides, wherein at leastabout 50 wt. % of the polysulfides are branched C₂₀ to C₆₀ polysulfidesrepresented by general formula R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is aninteger from 1 to 10, wherein R¹⁵ and R¹⁶ are each independently abranched C₁₀ to C₃₀ alkyl group represented by Structure K30-A,Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E,Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an S¹ atom of an R¹⁵S¹ group or an S² atom of an R¹⁶S² group,and wherein R⁹ is a C₁ to C₂₁ alkyl group; and (B) from at least about10 wt. % to at least about 30 wt. % monosulfides, wherein at least 50wt. % of the monosulfides are branched C₂₀ to C₆₀ monosulfidesrepresented by general formula R¹⁷—S—R¹⁸, wherein R¹⁷ and R¹⁸ are eachindependently a branched C₁₀ to C₃₀ alkyl group represented by StructureK30-A, Structure K30-B, Structure K30-C, Structure K30-D, StructureK30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an attachment point with a sulfur atom of the branched C₂₀ toC₆₀ monosulfide, and wherein R⁹ is a C₁ to C₂₁ alkyl group.

A thirty-first aspect which is a composition comprising: (A) at leastabout 25 wt. % branched C₂₀ to C₆₀ polysulfides represented by generalformula R¹⁵S¹—[S]_(n)—S²R¹⁶, wherein n is an integer from 1 to 10,wherein R¹⁵ and R¹⁶ are each independently a branched C₁₀ to C₃₀ alkylgroup represented by Structure K30-A, Structure K30-B, Structure K30-C,Structure K30-D, Structure K30-E, Structure K30-F, Structure K30-G, orStructure K30-H, wherein * designates an S¹ atom of an R¹⁵S¹ group or anS² atom of an R¹⁶S² group, and wherein R⁹ is a C₁ to C₂₁ alkyl group;and (B) at least about 5 wt. % branched C₂₀ to C₆₀ monosulfidesrepresented by general formula R¹⁷—S—R¹⁸, wherein R¹⁷ and R¹⁸ are eachindependently a branched C₁₀ to C₃₀ alkyl group represented by StructureK30-A, Structure K30-B, Structure K30-C, Structure K30-D, StructureK30-E, Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an attachment point with a sulfur atom of the branched C₂₀ toC₆₀ monosulfide, and wherein R⁹ is a C₁ to C₂₁ alkyl group; and one ormore of the following components (C)-(I): (C) less than about 5 wt. %branched C₁₆ polysulfides; (D) less than about 15 wt. % branched C₆₄polysulfides; (E) less than about 15 wt. % branched C₆₈ polysulfides;(F) less than about 5 wt. % branched C₇₂ polysulfides and/or branchedC₇₆ polysulfides; (G) less than about 1 wt. % branched C₁₆ to C₇₆monosulfides represented by general formula R¹⁷—S—R¹⁸, wherein R¹⁷ andR¹⁸ are each independently a functional group derived from an olefinselected from the group consisting of C₈ monoolefins, C₃₂ monoolefins,C₃₄ monoolefins, C₃₆ monoolefins, and C₃₈ monoolefins, wherein R¹⁷ andR¹⁸ are not both branched C₃₀ monoolefins; (H) less than about 10 wt. %unreacted C₈ to C₃₈ mercaptans; and (I) less than about 10 wt. %non-mercaptan impurities selected from the group consisting of C₈ to C₃₈olefins, C₈ to C₁₄ alkanes, cyclohexane, methylcyclopentane,methylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene,hexamethylbenzene, C₄ to C₁₂ alcohols, 2-ethyl-1-hexanol, and2-ethylhexyl-2-ethylhexanoate.

While aspects and embodiments of the disclosure have been shown anddescribed, modifications thereof can be made without departing from thespirit and teachings of the present disclosure. The embodiments andexamples described herein are exemplary only, and are not intended to belimiting. Many variations and modifications of the present disclosureare possible and are within the scope of the subject matter as disclosedherein.

At least one aspect or embodiment is disclosed and variations,combinations, and/or modifications of the embodiment(s) and/or featuresof the embodiment(s) made by a person having ordinary skill in the artare within the scope of the disclosure. Alternative aspects orembodiments that result from combining, integrating, and/or omittingfeatures of the embodiment(s) are also within the scope of thedisclosure. Where numerical ranges or limitations are expressly stated,such express ranges or limitations should be understood to includeiterative ranges or limitations of like magnitude falling within theexpressly stated ranges or limitations (e.g., from about 1 to about 10includes, 2, 3, 4, etc.; greater than 0.10 includes 0.11, 0.12, 0.13,etc.). For example, whenever a numerical range with a lower limit,R_(l), and an upper limit, R_(u), is disclosed, any number fallingwithin the range is specifically disclosed. In particular, the followingnumbers within the range are specifically disclosed:R=R_(l)+k·(R_(u)−R_(l)), wherein k is a variable ranging from 1 percentto 100 percent with a 1 percent increment, i.e., k is 1 percent, 2percent, 3 percent, 4 percent, 5 percent, . . . 50 percent, 51 percent,52 percent . . . 95 percent, 96 percent, 97 percent, 98 percent, 99percent, or 100 percent. Moreover, any numerical range defined by two Rnumbers as defined in the above is also specifically disclosed. Use ofthe term “optionally” with respect to any element of a claim means thatthe element is required, or alternatively, the element is not required,both alternatives being within the scope of the claim. Use of broaderterms such as comprises, includes, and having should be understood toprovide support for narrower terms such as consisting of, consistingessentially of, and comprised substantially of.

What is claimed is:
 1. A process of producing a polysulfides crudeproduct comprising one or more branched C₂₀ to C₆₀ polysulfidescomprising: (A) reacting a feedstock comprising one or more branched C₁₀to C₃₀ mercaptans and sulfur in the presence of a catalyst and (B)collecting the polysulfides crude product, and wherein (A) reactingfurther comprises: (a) contacting the one or more branched C₁₀ to C₃₀mercaptans and the catalyst to form a mixture wherein a weight ratio ofcatalyst to mercaptans is in a range of from about 0.005:1 to about0.013:1; (b) heating the mixture to a temperature in a range of fromabout 60° C. to about 85° C.; (c) heating the mixture to a temperaturein a range of from about 90° C. to about 150° C.; and (d) cooling themixture to a temperature in a range of from about 65° C. to about 85° C.2. The process of claim 1, wherein the one or more branched C₁₀ to C₃₀mercaptans are represented by Structure A-1, Structure B-1, StructureC-1, Structure D-1, Structure E-1, Structure F-1, Structure G-1,Structure H-1, or combinations thereof,

wherein R⁹ is a C₁ to C₂₁ alkyl group.
 3. The process of claim 1,wherein the one or more branched C₂₀ to C₆₀ polysulfides arepolysulfides represented by general formula R¹⁵S¹—[S]_(n)S²R¹⁶, whereinn is an integer from 1 to 10; R¹⁵ and R¹⁶ are each independently abranched C₁₀ to C₃₀ alkyl group represented by Structure K30-A,Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E,Structure K30-F, Structure K30-G, or Structure K30-H; wherein *designates an S¹ atom of an R¹⁵S¹ group or an S² atom of an R¹⁶S² group;and R⁹ is a C₁ to C₂₁ alkyl group.


4. The process of claim 1, wherein (B) collecting the crude productcomprises: (e) cooling the mixture to a temperature in a range of fromabout 20° C. to about 35° C.; and (f) filtering the polysulfides crudeproduct.
 5. The process of claim 1, wherein during step (b): (i) themixture is contacted with elemental sulfur wherein an equivalent molarratio of sulfur to mercaptans is in a range of from about 0.07:1 toabout 1.2:1; and (ii) the mixture is agitated for a time period of fromabout 2 hours to about 6 hours.
 6. The process of claim 1, whereinduring step (c): (i) the mixture is agitated for a time period of fromabout 2 hours to about 4 hours; and (ii) the mixture is sparged with aninert gas for a time period of from about 0.5 hour to about 4 hours. 7.The process of claim 1, wherein during step (d): (i) an epoxide is addedto the mixture over a time period of from about 10 min to about 2 hourswherein an equivalent molar ratio of epoxide to mercaptans is in a rangeof from about 0.05:1 to about 0.1:1; (ii) the mixture is agitated for atime period of from about 1 hour to about 4 hours; and (iii) the mixtureis sparged with an inert gas for a time period of from about 0.5 hour toabout 4 hours.
 8. The process of claim 7, wherein the epoxide comprisesethylene oxide, propylene oxide, or a combination thereof.
 9. Theprocess of claim 1, wherein the catalyst comprises: (i) a surfactant and(ii) a Group 1 or Group 2 metal hydroxide, wherein a weight ratio of (i)to (ii) is in a range of from about 25:1 to about 40:1.
 10. The processof claim 9, wherein prior to contacting the catalyst with the one ormore branched C₁₀ to C₃₀ mercaptans, (i) and (ii) are combined andheated to a temperature in a range of from about 60° C. to about 100° C.and the temperature is maintained for a time period of from about 30 minto about 2 hours.
 11. The process of claim 9, wherein the surfactantcomprises a nonionic surfactant.
 12. The process of claim 9, wherein thesurfactant comprises a polyethoxylated alcohol, a polyethoxylatedmercaptan, or a combination thereof.
 13. The process of claim 9, whereinthe Group 1 or Group 2 metal hydroxide is a solid or is dissolved in anaqueous solution.
 14. The process of claim 9, wherein the Group 1 orGroup 2 metal hydroxide is sodium hydroxide.
 15. The process of claim 1,wherein (A) reacting further comprises: (a) contacting the mixture withelemental sulfur wherein an equivalent molar ratio of sulfur tomercaptans is in a range of from about 0.07:1 to about 1.2:1; (b)maintaining the temperature of from about 60° C. to about 85° C. whilethe mixture is agitated for a time period of from about 2 hours to about6 hours; (c) maintaining the temperature in a range of from about 90° C.to about 150° C. while the mixture is agitated for a time period of fromabout 2 hours to about 4 hours and subsequently sparged with an inertgas for a time period of from about 0.5 hour to about 4 hours; and (d)maintaining the mixture at a temperature in a range of from about 65° C.to about 85° C. while: (i) an epoxide is added to the mixture over atime period of from about 10 min to about 2 hours wherein an equivalentmolar ratio of epoxide to mercaptans is in a range of from about 0.05:1to about 0.1:1; (ii) the mixture is agitated for a time period for atime period of from about 1 hour to about 4 hours; and (iii) the mixtureis sparged with an inert gas for a time period of from about 0.5 hour toabout 4 hours.
 16. The process of claim 1, wherein after cooling themixture (d), the process further comprises: (e) adding a decolorizingagent to the mixture, wherein a weight ratio of decolorizing agent tomercaptans is in a range of from about 0.01:1 to about 0.02:1; (f)heating the mixture to a temperature in a range of from about 40° C. toabout 60° C., and maintaining the temperature for a time period of fromabout 30 min to about 2 hours; (g) cooling the mixture to a temperaturein a range of from about 20° C. to about 35° C.; and (h) collecting thepolysulfides crude product.
 17. A process of producing a polysulfidescrude product comprising one or more branched C₂₀ to C₆₀ polysulfidescomprising: (A) reacting a feedstock comprising one or more branched C₁₀to C₃₀ mercaptans and sulfur in the presence of a catalyst and (B)collecting the polysulfides crude product, and wherein (B) collectingthe polysulfides crude product further comprises: (e) cooling themixture to a temperature in a range of from about 20° C. to about 35°C.; and (f) filtering the polysulfides crude product.
 18. The process ofclaim 1, wherein (A) reacting further comprises: (a) contacting the oneor more branched C₁₀ to C₃₀ mercaptans and the catalyst to form amixture wherein a weight ratio of catalyst to mercaptans is in a rangeof from about 0.005:1 to about 0.013:1; (b) heating the mixture to atemperature in a range of from about 60° C. to about 85° C.; (c) heatingthe mixture to a temperature in a range of from about 90° C. to about150° C.; and (d) cooling the mixture to a temperature in a range of fromabout 65° C. to about 85° C.
 19. The process of claim 17 wherein the oneor more branched C₁₀ to C₃₀ mercaptans are represented by Structure A-1,Structure B-1, Structure C-1, Structure D-1, Structure E-1, StructureF-1, Structure G-1, Structure H-1, or combinations thereof,

wherein R⁹ is a C₁ to C₂₁ alkyl group.
 20. The process of claim 17,wherein the one or more branched C₂₀ to C₆₀ polysulfides arepolysulfides represented by general formula R¹⁵S¹—[S]_(n)—S²R¹⁶, whereinn is an integer from 1 to 10; R¹⁵ and R¹⁶ are each independently abranched C₁₀ to C₃₀ alkyl group represented by Structure K30-A,Structure K30-B, Structure K30-C, Structure K30-D, Structure K30-E,Structure K30-F, Structure K30-G, or Structure K30-H, wherein *designates an S¹ atom of an R¹⁵S¹ group or an S² atom of an R¹⁶S² group;and R⁹ is a C₁ to C₂₁ alkyl group.


21. The process of claim 18, wherein during step (b): (i) the mixture iscontacted with elemental sulfur wherein an equivalent molar ratio ofsulfur to mercaptans is in a range of from about 0.07:1 to about 1.2:1;and (ii) the mixture is agitated for a time period of from about 2 hoursto about 6 hours.
 22. The process of claim 18, wherein during step (c):(i) the mixture is agitated for a time period of from about 2 hours toabout 4 hours; and (ii) the mixture is sparged with an inert gas for atime period of from about 0.5 hour to about 4 hours.
 23. The process ofclaim 18, wherein during step (d): an epoxide is added to the mixtureover a time period of from about 10 min to about 2 hours wherein anequivalent molar ratio of epoxide to mercaptans is in a range of fromabout 0.05:1 to about 0.1:1; (ii) the mixture is agitated for a timeperiod of from about 1 hour to about 4 hours; and (iii) the mixture issparged with an inert gas for a time period of from about 0.5 hour toabout 4 hours.
 24. The process of claim 23, wherein the epoxidecomprises ethylene oxide, propylene oxide, or a combination thereof. 25.The process of claim 17, wherein the catalyst comprises: (i) asurfactant and (ii) a Group 1 or Group 2 metal hydroxide, wherein aweight ratio of (i) to (ii) is in a range of from about 25:1 to about40:1.
 26. The process of claim 25, wherein prior to contacting thecatalyst with the one or more branched C₁₀ to C₃₀ mercaptans, (i) and(ii) are combined and heated to a temperature in a range of from about60° C. to about 100° C. and the temperature is maintained for a timeperiod of from about 30 min to about 2 hours.
 27. The process of claim25, wherein the surfactant comprises a nonionic surfactant.
 28. Theprocess of claim 25, wherein the surfactant comprises a polyethoxylatedalcohol, a polyethoxylated mercaptan, or a combination thereof.
 29. Theprocess of claim 25, wherein the Group 1 or Group 2 metal hydroxide is asolid or is dissolved in an aqueous solution.
 30. The process of claim25, wherein the Group 1 or Group 2 metal hydroxide is sodium hydroxide.31. The process of claim 17, wherein (A) reacting further comprises: (a)contacting the one or more branched C₁₀ to C₃₀ mercaptans and thecatalyst to form a mixture wherein a weight ratio of catalyst tomercaptans is in a range of from about 0.005:1 to about 0.013:1; (b)contacting the mixture with elemental sulfur wherein an equivalent molarratio of sulfur to mercaptans is in a range of from about 0.07:1 toabout 1.2:1; (c) heating the mixture to a temperature in a range of fromabout 60° C. to about 85° C. and maintaining the temperature while themixture is agitated for a time period of from about 2 hours to about 6hours; (d) heating the mixture to a temperature in a range of from about90° C. to about 150° C. and maintaining the temperature while themixture is agitated for a time period of from about 2 hours to about 4hours and subsequently sparged with an inert gas for a time period offrom about 0.5 hour to about 4 hours; and (e) cooling the mixture to atemperature in a range of from about 65° C. to about 85° C. andmaintaining the temperature while: (i) an epoxide is added to themixture over a time period of from about 10 min to about 2 hours whereinan equivalent molar ratio of epoxide to mercaptans is in a range of fromabout 0.05:1 to about 0.1:1; (ii) the mixture is agitated for a timeperiod for a time period of from about 1 hour to about 4 hours; and(iii) the mixture is sparged with an inert gas for a time period of fromabout 0.5 hour to about 4 hours.
 32. The process of claim 18, whereinafter cooling the mixture (d), the process further comprises: (e) addinga decolorizing agent to the mixture, wherein a weight ratio ofdecolorizing agent to mercaptans is in a range of from about 0.01:1 toabout 0.02:1; (f) heating the mixture to a temperature in a range offrom about 40° C. to about 60° C., and maintaining the temperature for atime period of from about 30 min to about 2 hours; (g) cooling themixture to a temperature in a range of from about 20° C. to about 35°C.; and (h) collecting the polysulfides crude product.